Hyperbranched olefin oil-based dielectric fluid

ABSTRACT

The present invention generally relates to a dielectric composition which is a poly-α-olefin or poly(co-ethylene-α-olefin) having a backbone weight average molecular weight less than 10,000 daltons. The dielectric composition uses a metal-ligand complex as a precatalyst and exhibits a hyperbranched structure that enables low viscosity, and therefore good flow characteristics, combined with high fire point due to ability to increase molecular weight via branching rather than backbone growth. Other desirable properties include lowered pour point due to crystallization disruption, and desirable thermal oxidative stability.

This application is a non-provisional application claiming priority from the U.S. Provisional Patent Application No. 61/581,402, filed on Dec. 29, 2011, entitled “Hyperbranched Olefin Oil Based Dielectric Fluid,” the teachings of which are incorporated by reference herein as if reproduced in full hereinbelow.

The present invention relates to a process to polymerize α-olefin or to copolymerize an α-olefin with ethylene. More particularly, it relates to a process for preparing dielectric fluids, particularly transformer fluids, which are hyperbranched oils.

The primary function of transformers is to raise or lower the alternating voltage in a substation according to requirements in order to transmit electricity at a low loss over long distances via transmission and distribution lines. During this process the transformer becomes hot, and this heat must be dissipated by means of a liquid coolant.

Thermal management of transformers is very critical for the safety of transformer operation. Although conventional transformers operate efficiently at relatively high temperatures, excessive heat is detrimental to transformer life. This is because transformers contain electrical insulation which is utilized to prevent energized components or conductors from contacting or arcing over the other components, conductor or other internal circuitry. Heat degrades insulation, causing it to lose its ability to perform its intended insulation function. The higher the temperature experienced by the insulation, the shorter the life of the insulation. When insulation fails, an internal fault or short circuit may occur. To prevent excessive temperature rise and premature transformer failure, transformers are generally filled with a liquid coolant to dissipate the relatively large quantities of heat generated during normal transformer operation. The coolant also functions to electrically insulate the transformer components as a dielectric medium. The dielectric liquid must be able to perform to cool and insulate for the service life of the transformer (e.g., over 20 or more years). Because dielectric fluids cool the transformer by convection, the viscosity of a dielectric fluid at various temperatures is one of the key factors in determining its efficiency.

In recent years, mineral oils have been widely used for this purpose, because they are good electrical insulators and also have a high thermal conductivity. However, they are also significantly flammable, which raises a safety issue in indoor, factory and underground operations.

In view of these needs, it is desirable in the art to provide dielectric fluids that are able to balance desirable flow behaviors at normal operation temperatures, which may include a wide temperature range; a high fire point, preferably above 200° C.; and desirable thermal oxidation stability, so that the dielectric fluid maintains its effectiveness over a considerable time period despite its role to continually or frequently dissipate large amounts of heat. In addition it is desirable that the dielectric fluid be relatively economical and conveniently or efficiently prepared.

In one aspect, the present invention is a dielectric fluid composition comprising a poly-α-olefin or a poly(co-ethylene/α-olefin) having a weight average molecular weight more than 200 and less than 10,000 daltons (Da) prepared from a process including a step of contacting together (1) a monomer selected from (a) an α-olefin; or (b) a combination of an α-olefin and ethylene; and (2) a catalytic amount of a catalyst wherein the catalyst includes a mixture or reaction product of ingredients (2a) and (2b) that is prepared before the contacting step, wherein ingredient (2a) is at least one metal-ligand complex of formula (I):

-   wherein M is titanium, zirconium, or hafnium, each independently     being in a formal oxidation state of +2, +3, or +4; n is an integer     of from 0 to 3, wherein when n is 0, X is absent; each X     independently is a monodentate ligand that is neutral, monoanionic,     or dianionic, or two X are taken together to form a bidentate ligand     that is neutral, monoanionic, or dianionic; X and n are chosen in     such a way that the metal-ligand complex of formula (I) is, overall,     neutral; each Z independently is O, S, N(C₁-C₄₀)hydrocarbyl, or     P(C₁-C₄₀)hydrocarbyl; L is (C₁-C₄₀)hydrocarbylene or     (C₁-C₄₀)heterohydrocarbylene, wherein the (C₁-C₄₀)hydrocarbylene has     a portion that comprises a 2-carbon atom linker backbone linking the     Z atoms in formula (I) and the (C₁-C₄₀)heterohydrocarbylene has a     portion that comprises a 2-atom atom linker backbone linking the Z     atoms in formula (I), wherein each atom of the 2-atom linker of the     (C₁-C₄₀)heterohydrocarbylene independently is a carbon atom or a     heteroatom, wherein each heteroatom independently is O, S, S(O),     S(O)₂, Si(R^(C))₂, Ge(R^(C))₂, P(R^(P)), or N(R^(N)), wherein     independently each R^(C) is unsubstituted (C₁-C₁₈)hydrocarbyl or the     two R^(C) are taken together to form a (C₂-C₁₉)alkylene, each R^(P)     is unsubstituted (C₁-C₁₈)hydrocarbyl; and each R^(N) is     unsubstituted (C₁-C₁₈)hydrocarbyl, a hydrogen atom or absent;     R^(1a), R^(2a), R^(1b), and R^(2b) independently is a hydrogen,     (C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, N(R^(N))₂, NO₂,     OR^(C), SR^(C), Si(R^(C))₃, Ge(R^(C))₃, CN, CF₃, F₃CO, halogen atom;     and each of the others of R^(1a), R^(2a), R^(1b), and R^(2b)     independently is a hydrogen, (C₁-C₄₀)hydrocarbyl,     (C₁-C₄₀)heterohydrocarbyl, N(R^(N))₂, NO₂, OR^(C), SR^(C),     Si(R^(C))₃, CN, CF₃, F₃CO or halogen atom; each of R^(3a), R^(4a),     R^(3b), R^(4b), R^(6c), R^(7c), R^(8c), R^(6d), R^(7d) and R^(8d)     independently is a hydrogen atom; (C₁-C₄₀)hydrocarbyl;     (C₁-C₄₀)heterohydrocarbyl; Si(R^(C))₃, Ge(R^(C))₃, P(R^(P))₂,     N(R^(N))₂, OR^(C), SR^(C), NO₂, CN, CF₃, R^(C)S(O)—, R^(C)S(O)₂—,     (R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—, R^(C)C(O)N(R)—,     (R^(C))₂NC(O)— or halogen atom; each of R^(5c) and R^(5d)     independently is a (C₆-C₄₀)aryl or (C₁-C₄₀)hetero-aryl; each of the     aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl,     hydrocarbylene, and heterohydro-carbylene groups independently is     unsubstituted or substituted with one or more substituents R^(S);     and each R^(S) independently is a halogen atom, polyfluoro     substitution, perfluoro substitution, unsubstituted (C₁-C₁₈)alkyl,     F₃C—, FCH₂O—, F₂HCO—, F₃CO—, R₃Si—, R₃Ge—, RO—, RS—, RS(O)—,     RS(O)₂—, R₂P—, R₂N—, R₂C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or     R₂NC(O)—, or two of the R^(S) are taken together to form an     unsubstituted (C₁-C₁₈)alkylene, wherein each R independently is an     unsubstituted (C₁-C₁₈)alkyl; and wherein ingredient (2b) is at least     one activating co-catalyst, such that the ratio of total number of     moles of the at least one metal-ligand complex (2a) to total number     of moles of the at least one activating co-catalyst (2b) is from     1:10,000 to 100:1; under conditions such that a product selected     from a poly-α-olefin and a poly(co-ethylene-α-olefin) is formed, the     product having molecular weight distribution components and a     backbone weight average molecular weight (Mw) that are more than 200     Da and less than 10,000 Da, the product including at least two     isomers in each distribution component above 300 Da.

The invention offers novel dielectric fluid compositions comprising poly-α-olefin or poly(co-ethylene-α-olefin) using as a catalyst one or more of a group of compounds having a two-atom bridge between bis-ether oxygen atoms. These catalysts have been found to afford a unique capability to produce low molecular weight polymers with unique isomer distribution where there are at least two isomers for each distribution component above 300 Da and at least three isomers for each distribution component above 400 dalton. By “distribution component” is meant a single given molecular species, including all of its isomers Examples of such may include dimers, trimers, tetramers, et cetera. These low molecular weight polymers include both poly-α-olefins and poly(co-ethylene/α-olefins), generally having molecular weights more than 200 and less than 10,000 Da, preferably less than 5,000 Da. Processing may be accomplished over a wide temperature range, from 40° C. to 300° C. Because of their relatively low molecular weights, these products exhibit controlled viscosity and are generally liquids, increasing the number of potential applications for them. Even more important, the products exhibit unique structural and property relationships that make them particularly useful as dielectric fluids.

Importantly, these compositions are structurally hyperbranched polyolefin liquids, wherein the viscosity thereof actually decreases as the backbone chain length decreases. At the same time, the fire point increases as the molecular weight of the dielectric fluid composition increases. This combination enables the possibility to build molecular weight by increasing the number of branches, while at the same time controlling hydrodynamic volume and therefore viscosity by minimizing the size of the carbon backbone. The result is a higher fire point, well above the expected range of linear hydrocarbon liquids such as mineral oils, and a considerably lowered pour point due to disruption of crystallization caused by the hindered chain packing due to the hyperbranched structure. These highly desirable qualities enable use of the dielectric fluid compositions of the invention in applications including, but not limited to, transformer oils, transmission and distribution cable insulation fluids, switchgear fluids, dielectric fluids for telecommunication cables, insulation fluids for bushings, dielectric fluids for electronic devices such as for circuit boards, and dielectric fluids for electrical apparatus such as motors and generators. For convenience herein, all of the above and related applications are deemed to fall within the generalized phrase “dielectric fluid composition(s).”

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a GC-MS chromatograph of a sample from Example 4.

FIG. 2 is a GC-MS chromatograph of a sample from Example 5.

Preparation of the low molecular weight poly-α-olefins or poly(co-ethylene-α-olefins) (i.e., ethylene/α-olefin copolymers) herein is generally by contact between the selected catalyst or catalysts and the other starting ingredients, with a first step comprising contacting the metal-ligand complex with a suitable activating co-catalyst to form a catalyst, followed by contact between the catalyst, or catalysts, and the selected monomeric material(s) under suitable reaction conditions to form the final desired product.

In general the catalysts useful in the present invention fall within the group defined by co-pending U.S. Publication No. 2011/0282018 A1, filed May 11, 2011. However, the catalysts used herein form a subset thereof that exhibits surprising capabilities not shared by other members of that group, notably to form the dielectric fluid compositions of the present invention.

In some embodiments, each of the chemical groups (e.g., X, L, R^(1a), etc.) of the metal-ligand complex of formula (I) is unsubstituted, that is, can be defined without use of a substituent R^(S). In other embodiments, at least one of the chemical groups of the metal-ligand complex independently contains one or more of the substituents R^(S). Preferably, there are not more than a total of 20 R^(S), more preferably not more than 10 R^(S), and still more preferably not more than 5 R^(S). Where the invention compound contains two or more substituents R^(S), each R^(S) independently is bonded to a same or different substituted chemical group. When two or more R^(S) are bonded to a same chemical group, they independently are bonded to a same or different carbon atom or heteroatom in the same chemical group, up to and including persubstitution of the chemical group.

The term “persubstitution” means each hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R^(S)). The term, “polysubstitution” means at least two, but not all, hydrogen atoms (H) bonded to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional group are replaced by substituents (e.g., R^(S)). In some embodiments, at least one R^(S) is polyfluoro substitution or perfluoro substitution.

As used herein, “polyfluoro substitution” and “perfluoro substitution” each count as one R^(S) substituent. In some embodiments each R^(S) independently is selected from a group consisting of a halogen atom and any one of polyfluoro substitution, unsubstituted (C₁-C₁₈)alkyl, F₃C—, FCH₂O—, F₂HCO—, F₃CO—, R₃Si—, R₃Ge—, RO—, RS—, RS(O)—, RS(O)₂—, R₂P—, R₂N—, R₂C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, and R₂NC(O)—, wherein each R independently is an unsubstituted (C₁-C₁₈)alkyl. In some embodiments each R^(S) independently is selected from a group consisting of a halogen atom, unsubstituted (C₁-C₁₈)alkyl, and any one of polyfluoro substitution, F₃C—, FCH₂O—, F₂HCO—, F₃CO—, R₃Si—, R₃Ge—, RO—, RS—, RS(O)—, RS(O)₂—, R₂P—, R₂N—, R₂C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, and R₂NC(O)—. In some embodiments each R^(S) independently is selected from a group consisting of an unsubstituted (C₁-C₁₈)alkyl and any one of F₃C—, FCH₂O—, F₂HCO—, F₃CO—, R₃Si—, R₃Ge—, RO—, RS—, RS(O)—, RS(O)₂—, R₂P—, R₂N—, R₂C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, and R₂NC(O)—. In some embodiments two R^(S) are taken together to form an unsubstituted (C₁-C₁₈)alkylene. Still more preferably substitutents R^(S) independently are unsubstituted (C₁-C₁₈)alkyl, F, unsubstituted (C₁-C₁₈)alkylene, or a combination thereof; and even more preferably unsubstituted (C₁-C₈)alkyl or unsubstituted (C₁-C₈)alkylene. The (C₁-C₁₈)alkylene and (C₁-C₈)alkylene substituents are especially useful for forming substituted chemical groups that are bicyclic or tricyclic analogs of corresponding monocyclic or bicyclic unsubstituted chemical groups.

The term “hydrocarbylene” means a hydrocarbon diradical having at least one carbon atom, such that each hydrocarbon diradical independently is aromatic or non-aromatic; saturated or unsaturated; straight chain or branched chain; cyclic or acyclic; unsubstituted or substituted; or a combination of at least two thereof. The radicals of the hydrocarbon diradical can be on a single carbon atom or, preferably, different carbon atoms. The term “alkylene” is a hydrocarbylene wherein the hydrocarbon diradical is non-aromatic, saturated, straight chain or branched, acyclic, and unsubstituted or substituted. The term “hydrocarbyl” is as defined previously for hydrocarbylene, except where hydrocarbylene is the diradical, the hydrocarbyl is a monoradical and thus has a hydrogen atom in place of the second radical of the diradical. The term “alkyl” is a hydrocarbyl wherein the hydrocarbon radical is non-aromatic, saturated, straight chain or branched, acyclic, and unsubstituted or substituted. Preferably, the substituent of the substituted alkyl is aryl. The term “heterohydrocarbylene” means a heterohydrocarbon diradical having at least one carbon atom and from 1 to 6 heteroatoms, wherein each heterohydrocarbon diradical independently is aromatic or non-aromatic; saturated or unsaturated; straight chain or branched chain; cyclic or acyclic; unsubstituted or substituted; or a combination of at least two thereof. The radicals of the heterohydrocarbon diradical can be on a single atom or, preferably, different atoms, each radical-bearing atom independently being carbon or heteroatom. The term “heterohydrocarbyl” is as defined previously for heterohydrocarbylene, except where heterohydrocarbylene is the diradical, the heterohydrocarbyl is a monoradical.

In some embodiments the present invention contemplates such unsubstituted chemical groups or molecules having a lower limit of at least 1 carbon atom. However, the invention includes embodiments having higher lower limits (e.g., at least any one of 2, 3, 4, 5, 6, 7, and 8 carbons). In particular, embodiments including higher lower limits as would be well known for a smallest aspect of the chemical group or molecule (e.g., at least 3 carbons for a cycloalkyl or α-olefin) may be particularly preferred.

Preferably, each hydrocarbyl independently is an unsubstituted or substituted alkyl, cycloalkyl (having at least 3 carbon atoms), (C₃-C₂₀)cycloalkyl-(C₁-C₂₀)alkylene, aryl (having at least 6 carbon atoms), or (C₆-C₂₀)aryl-(C₁-C₂₀)alkylene. Preferably, each of the aforementioned hydrocarbyl groups independently has a maximum of 40, more preferably 20, and still more preferably 12 carbon atoms.

Preferably, each alkyl independently has a maximum of 40, more preferably 20, still more preferably 12, and still more preferably 8 carbon atoms. A few non-limiting examples of unsubstituted (C₁-C₄₀)alkyl include unsubstituted (C₁-C₂₀)alkyl; unsubstituted (C₁-C₁₀)alkyl; unsubstituted (C₁-C₅)alkyl; methyl; ethyl; 1-propyl; 2-methylpropyl; 1,1-dimethylethyl; and 1-heptyl. Non-limiting examples of substituted (C₁-C₄₀)alkyl include substituted (C₁-C₂₀)alkyl, substituted (C₁-C₁₀)alkyl, trifluoromethyl, and (C₄₅)alkyl. The (C₄₅)alkyl may be, for example, a (C₂₇-C₄₀)alkyl substituted by one R^(S), which is a (C₁₈-C₅)alkyl, respectively. Preferably, each (C₁-C₅)alkyl independently is methyl, trifluoromethyl, ethyl, 1-propyl, 2-methylethyl, or 1,1-dimethylethyl.

Preferably, each aryl independently has from 6 to 40 carbon atoms. The term “(C₆-C₄₀)aryl” means an unsubstituted or substituted (by at least one R^(S)) mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 40, preferably from 6 to 14, ring carbon atoms, and the mono-, bi- or tricyclic radical comprises 1, 2 or 3 rings, respectively, wherein the 1 ring is aromatic; at least one of the 2 or 3 rings is aromatic; and the 2 or 3 rings independently are fused or non-fused. Other aryl groups (e.g., (C₆-C₁₀)aryl)) are defined in an analogous manner. Preferably, (C₆-C₄₀)aryl has a maximum of 20 carbon atoms (i.e., (C₆-C₂₀)aryl), more preferably 10 carbon atoms, and still more preferably 6 carbon atoms. Non-limiting examples of unsubstituted (C₆-C₄₀)aryl include unsubstituted (C₆-C₂₀)aryl; unsubstituted (C₆-C₁₈)aryl; phenyl; (C₃-C₆)cycloalkyl-phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C₆-C₄₀)aryl are substituted (C₆-C₂₀)aryl; substituted (C₆-C₁₈)aryl; 2-(C₁-C₅)alkyl-phenyl; 2,4-bis(C₁-C₅)alkyl-phenyl; 2,4-bis[(C₂₀)alkyl]-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-1-yl.

Preferably, each cycloalkyl independently has from 3 to 40 carbon atoms. The term “(C₃-C₄₀)cycloalkyl” means a saturated cyclic hydrocarbon radical of from 3 to 40 carbon atoms that is unsubstituted or substituted by at least one R^(S). Other cycloalkyl groups (e.g., (C₃-C₁₂)alkyl)) are defined in an analogous manner. Preferably, (C₃-C₄₀)cycloalkyl has a maximum of 20 carbon atoms (i.e., (C₃-C₃₀)cycloalkyl), and more preferably 6 carbon atoms. Non-limiting examples of unsubstituted (C₃-C₄₀)cycloalkyl include unsubstituted (C₃-C₂₀)cycloalkyl, unsubstituted (C₃-C₁₀)cycloalkyl, cyclopropyl, and cyclodecyl. Examples of substituted (C₃-C₄₀)cycloalkyl are substituted (C₃-C₂₀)cycloalkyl, substituted (C₃-C₁₀)cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

Preferably, each hydrocarbylene independently has from 1 to 40 carbon atoms. Examples of (C₁-C₄₀)hydrocarbylene are unsubstituted or substituted (C₆-C₄₀)arylene, (C₃-C₄₀)cycloalkylene, and (C₁-C₄₀)alkylene (e.g., (C₁-C₂₀)alkylene). In some embodiments, the diradicals are on a same carbon atom (e.g., —CH₂—) or on adjacent carbon atoms (i.e., 1,2-diradicals), or are spaced apart by one, two, etc., intervening carbon atoms (e.g., respective 1,3-diradicals, 1,4-diradicals, etc.). Preferred is a 1,2-, 1,3-, 1,4-, or an α-, ω-diradical, and more preferably a 1,2-diradical. The α-, ω-diradical is a diradical that has a maximum carbon backbone spacing between the radical carbons. More preferred is a 1,2-diradical version of (C₆-C₁₈)arylene, (C₃-C₂₀)cycloalkylene, or (C₂-C₂₀)alkylene; a 1,3-diradical version of (C₆-C₁₈)arylene, (C₄-C₂₀)cycloalkylene, or (C₃-C₂₀)alkylene; or a 1,4-diradical version of (C₆-C₁₈)arylene, (C₆-C₂₀)cycloalkylene, or (C₄-C₂₀)alkylene.

Preferably, each alkylene independently has from 1 to 40 carbon atoms. The term “(C₁-C₄₀)alkylene” means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 40 carbon atoms that is unsubstituted or substituted by at least one R^(S). Other alkylene groups (e.g., (C₁-C₁₂)alkylene)) are defined in an analogous manner. Examples of unsubstituted (C₁-C₄₀)alkylene are unsubstituted (C₁-C₂₀)alkylene, including unsubstituted 1,2-(C₂-C₁₀)alkylene; 1,3-(C₃-C₁₀)alkylene; 1,4-(C₄-C₁₀)alkylene; —CH₂—, —CH₂CH₂—, —(CH₂)₃—, —CH₂CHCH₃, —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—, —(CH₂)₇—, —(CH₂)₈—, and —(CH₂)₄C(H)(CH₃)—. Examples of substituted (C₁-C₄₀)alkylene are substituted (C₁-C₂₀)alkylene, —CF₂—, —C(O)—, and —(CH₂)₁₄C(CH₃)₂(CH₂)₅— (i.e., a 6,6-dimethyl substituted normal-1,20-eicosylene). Since as mentioned previously two R^(S) may be taken together to form a (C₁-C₁₈)alkylene, examples of substituted (C₁-C₄₀)alkylene also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

Preferably, each cycloalkylene independently has from 3 to 40 carbon atoms. The term “(C₃-C₄₀)cycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) that is unsubstituted or substituted by at least one R^(S). Examples of unsubstituted (C₃-C₄₀)cycloalkylene are 1,3-cyclopropylene, 1,1-cyclopropylene, and 1,2-cyclohexylene. Examples of substituted (C₃-C₄₀)cycloalkylene are 2-oxo-1,3-cyclopropylene and 1,2-dimethyl-1,2-cyclohexylene.

Preferably, each heterohydrocarbyl independently has from 1 to 40 carbon atoms. The term “(C₁-C₄₀)heterohydrocarbyl” means a heterohydrocarbon radical and the term “(C₁-C₄₀)heterohydrocarbylene” means a heterohydrocarbon diradical, and each heterohydrocarbon independently has at least one heteroatom B(R^(C)) O; S; S(O); S(O)₂; Si(R^(C))₂; Ge(R^(C))₂; P(R^(P)); and N(R^(N)), wherein independently each R^(C) is unsubstituted (C₁-C₁₈)hydrocarbyl, each R^(P) is unsubstituted (C₁-C₁₈)hydrocarbyl; and each R^(N) is unsubstituted (C₁-C₁₈)hydrocarbyl or absent (e.g., absent when N comprises —N═ or tri-carbon substituted N). The radicals of the diradical can be on same or different type of atoms (e.g., both on saturated acyclic atoms or one on an acyclic atom and one on aromatic atom). Other heterohydrocarbyl (e.g., (C₁-C₁₂) heterohydrocarbyl)) and heterohydrocarbylene groups are defined in an analogous manner. Preferably, the heteroatom(s) is O; S; S(O); S(O)₂; Si(R^(C))₂; P(R^(P)); or N(R^(N)). The heterohydrocarbon radical and each of the heterohydrocarbon diradicals independently is on a carbon atom or heteroatom thereof, although preferably each is on a carbon atom when bonded to a heteroatom in formula (I) or to a heteroatom of another heterohydrocarbyl or heterohydrocarbylene. Each (C₁-C₄₀)heterohydrocarbyl and (C₁-C₄₀)heterohydrocarbylene independently is unsubstituted or substituted (by at least one R^(S)), aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic) or acyclic, or a combination of two or more thereof; and each is respectively the same as or different from another.

Preferably, each heteroaryl independently has from 1 to 40 carbon atoms. The term “(C₁-C₄₀)heteroaryl” means an unsubstituted or substituted (by at least one R^(S)) mono-, bi- or tricyclic heteroaromatic hydrocarbon radical of from 1 to 40 total carbon atoms and from 1 to 4 heteroatoms; from 1 to 44 total ring atoms, preferably from 5 to 10 total ring atoms, and the mono-, bi- or tricyclic radical comprises 1, 2 or 3 rings, respectively, wherein the 1-ring is heteroaromatic; at least one of the 2 or 3 rings is heteroaromatic; and the 2 or 3 rings independently are fused or non-fused. Other heteroaryl groups (e.g., (C₁-C₁₂)heteroaryl)) are defined in an analogous manner. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered ring has from 1 to 4 carbon atoms and from 4 to 1 heteroatoms, respectively, each heteroatom being O, S, N, or P, and preferably O, S, or N. Examples of 5-membered ring heteroaromatic hydrocarbon radical are pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 4 or 5 carbon atoms and 2 or 1 heteroatoms, the heteroatoms being N or P, and preferably N. Examples of 6-membered ring heteroaromatic hydrocarbon radical are pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical preferably is a fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol-1-yl; and benzimidazole-1-yl. Examples of the fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical preferably is a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring system. An example of the fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-ƒ]indol-1-yl. An example of the fused 5,6,6-ring system is 1H-benzo[ƒ]indol-1-yl. An example of the fused 6,5,6-ring system is 9H-carbazol-9-yl, which may also be named as a dibenzo-1H-pyrrole-1-yl. An example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of the fused 6,6,6-ring system is acrydin-9-yl. The 5-membered rings and 6-membered rings of the fused 5,6-; 6,6-; 5,6,5-; 5,6,6-; 6,5,6-; and 6,6,6-ring systems independently can be as described above for 5-membered and 6-membered rings, respectively, except where the ring fusions occur.

The aforementioned heteroalkyl and heteroalkylene groups are saturated straight or branched chain radicals or diradicals, respectively, containing at least one carbon atom and at least one heteroatom (up to 4 heteroatoms) Si(R^(C))₂, Ge(R^(C))₂, P(R^(P)), N(R^(N)), N, O, S, S(O), and S(O)₂ as defined above, wherein each of the heteroalkyl and heteroalkylene groups independently are unsubstituted or substituted by at least one R^(S).

Unless otherwise indicated herein the term “heteroatom” means O, S, S(O), S(O)₂, Si(R^(C))₂, Ge(R^(C))₂, P(R^(P)), or N(R^(N)), wherein independently each R^(C) is unsubstituted (C₁-C₁₈)hydrocarbyl or the two R^(C) are taken together to form a (C₂-C₁₉)alkylene (e.g., the two R^(C) together with the silicon atom to which they are both bonded form a 3-membered to 20-membered silacycloalkyl), each R^(P) is unsubstituted (C₁-C₁₈)hydrocarbyl; and each R^(N) is unsubstituted (C₁-C₁₈)hydrocarbyl, a hydrogen atom, or absent (absent when N comprises —N═ as in a N-containing heteroaryl).

Preferably, there are no O—O, S—S, or O—S bonds, other than O—S bonds in an S(O) or S(O)₂ diradical functional group, in the metal-ligand complex of formula (I). More preferably, there are no O—O, N—N, P—P, N—P, S—S, or O—S bonds, other than O—S bonds in an S(O) or S(O)₂ diradical functional group, in the metal-ligand complex of formula (I).

The term “saturated” means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. Where a saturated chemical group is substituted by one or more substituents R^(S), one or more double and/or triple bonds optionally may or may not be present in substituents R^(S). The term “unsaturated” means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds, not including any such double bonds that may be present in substituents R^(S), if any, or in (hetero)aromatic rings, if any.

In the metal-ligand complex of formula (I) certain variables and chemical groups n, M, X, Z, L, R^(1a), R^(2a), R^(3a), R^(4a), R^(1b), R^(2b), R^(3b), R^(4b), R^(5c), R^(6c), R^(7c), R^(8c), R^(5d), R^(6d), R^(7d), and R^(8d), as the formulas allow, are preferred. Examples of such preferred groups follow.

Preferably M is zirconium or hafnium, and more preferably M is zirconium. The formal oxidation state of M may vary as +2 or +4. Any combination of a preferred M and a preferred formal oxidation state may be employed.

In various embodiments n may be 0, 1, 2, or 3.

Certain X groups are preferred. In some embodiments each X independently is the monodentate ligand. Preferably when there are two or more X monodentate ligands, each X is the same. In some embodiments the monodentate ligand is the monoanionic ligand. The monoanionic ligand has a net formal oxidation state of −1. Each monoanionic ligand preferably independently is hydride, hydrocarbyl carbanion, heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(O)O⁻, hydrocarbylC(O)O⁻, HC(O)N(H)⁻, hydrocarbylC(O)N(H)⁻, hydrocarbylC(O)N—(C₁-C₂₀)hydrocarbyl)⁻, R^(K)R^(L)B⁻, R^(K)R^(L)N⁻, R^(K)O⁻, R^(K)S⁻, R^(K)R^(L)P⁻, or R^(M)R^(K)R^(L)Si⁻, wherein each R^(K), R^(L), and R^(M) independently is hydrogen, hydrocarbyl, or heterohydrocarbyl, or R^(K) and R^(L) are taken together to form a (C₂-C₄₀)hydrocarbylene or heterohydrocarbylene and R^(M) is as defined above.

In some embodiments at least one monodentate ligand of X independently is the neutral ligand. Preferably the neutral ligand is a neutral Lewis base group that is R^(X)NR^(K)R^(L), R^(K)OR^(L), R^(K)SR^(L), or R^(X)PR^(K)R^(L), wherein each R^(X) independently is hydrogen, hydrocarbyl, [(C₁-C₁₀)hydrocarbyl]₃Si, [(C₁-C₁₀)hydrocarbyl]₃Si—(C₁-C₁₀)hydrocarbyl, or heterohydrocarbyl and each R^(K) and R^(L) independently is as defined above.

In some embodiments, each X is a monodentate ligand that independently is a halogen atom, unsubstituted (C₁-C₂₀)hydrocarbyl, unsubstituted (C₁-C₂₀)hydrocarbylC(O)O—, or R^(K)R^(L)N— wherein each of R^(K) and R^(L) independently is an unsubstituted (C₁-C₂₀)hydrocarbyl. In some embodiments each monodentate ligand X is a chlorine atom, (C₁-C₁₀)hydrocarbyl (e.g., (C₁-C₆)alkyl or benzyl), unsubstituted (C₁-C₁₀)hydrocarbylC(O)O—, or R^(K)R^(L)N— wherein each of R^(K) and R^(L) independently is an unsubstituted (C₁-C₁₀)hydrocarbyl.

In some embodiments there are at least two X and the two X are taken together to form the bidentate ligand. In some embodiments the bidentate ligand is a neutral bidentate ligand. Preferably the neutral bidentate ligand is a diene of formula (R^(D))₂C═C(R^(D))—C(R^(D))═C(R^(D))₂, wherein each R^(D) independently is H, unsubstituted (C₁-C₆)alkyl, phenyl, or naphthyl. In some embodiments the bidentate ligand is a monoanionic-mono(Lewis base) ligand. The monoanionic-mono(Lewis base) ligand preferably is a 1,3-dionate of formula (D): R^(E)—C(O⁻)═CH—C(═O)—R^(E) (D), wherein each R^(D) independently is H, unsubstituted (C₁-C₆)alkyl, phenyl, or naphthyl. In some embodiments the bidentate ligand is a dianionic ligand. The dianionic ligand has a net formal oxidation state of −2. Preferably each dianionic ligand independently is carbonate, oxalate (i.e., ^(−O) ₂CC(O)O⁻), (C₂-C₄₀)hydrocarbylene dicarbanion, heterohydrocarbylene dicarbanion, phosphate, or sulfate.

As previously mentioned, number and charge (neutral, monoanionic, dianionic) of X are selected depending on the formal oxidation state of M such that the metal-ligand complex of formula (I) is, overall, neutral.

In some embodiments each X is the same, wherein each X is methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chloro. In some embodiments n is 2 and each X is the same.

In some embodiments at least two X are different. In some embodiments n is 2 and each X is a different one of methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chloro.

The integer n indicates number of X. Preferably n is 2 or 3 and at least two X independently are monoanionic monodentate ligands and a third X, if present, is a neutral monodentate ligand. In some embodiments n is 2 at two X are taken together to form a bidentate ligand. In some embodiments the bidentate ligand is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

In some embodiments L is two-carbon atom hydrocarbylene. In some embodiments L comprises the 2-carbon atom linker backbone (e.g., L is —CH₂CH₂—, —CH═CH— or —CH(CH₃)CH(CH₃)—). In some embodiments L is the unsubstituted alkylene, and more preferably L is an acyclic unsubstituted alkylene, and still more preferably the acyclic unsubstituted alkylene is —CH₂CH₂—, —CH₂CH(CH₂)—, cis-CH(CH₃)CH(CH₃)—, or trans-CH(CH₃)CH(CH₃)—.

In some embodiments L is the unsubstituted 1,2-cycloalkylene, and more preferably L is cis-1,2-cyclopentane-diyl or cis-1,2-cyclohexane-diyl. In some embodiments L is the substituted cycloalkylene.

In some embodiments L is substituted or unsubstituted two-atom heterohydrocarbylene. In some embodiments L comprises the 2-atom linker backbone (e.g., L is —CH₂CH(OCH₃)— or —CH₂Si(CH₃)₂—).

Certain R^(1a), R^(2a), R^(1b), and R^(2b) groups are preferred. In some embodiments one of R^(1a), R^(2a), R^(1b), and R^(2b) independently is a hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom; and each of the others of R^(1a), R^(2a), R^(1b), and R^(2b) is a hydrogen atom. In some such embodiments it is each of R^(2a), R^(1b), and R^(2b) that is a hydrogen atom. In other such embodiments it is each of R^(1a), R^(1b), and R^(2b) that is a hydrogen atom.

In some embodiments two of R^(1a), R^(2a), R^(1b), and R^(2b) independently are a hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom; and each of the others of R^(1a), R^(2a), R^(1b), and R^(2b) is a hydrogen atom. In some such embodiments it is each of R^(1b) and R^(2b) that is a hydrogen atom. In other such some embodiments it is each of R^(2a) and R^(2b) that is a hydrogen atom. In still other such some embodiments it is each of R^(1a) and R^(1b) that is a hydrogen atom.

In some embodiments three of R^(1a), R^(2a), R^(1b), and R^(2b) independently are a hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom; and the other of R^(1a), R^(2a), R^(1b), and R^(2b) is a hydrogen atom. In some such embodiments it is R^(1b) that is a hydrogen atom. In other such some embodiments it is R^(2b) that is a hydrogen atom.

In some embodiments each of R^(1a), R^(2a), R^(1b), and R^(2b) independently is a hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom.

In some embodiments one of R^(1a) and R^(1b) independently is a hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom, and the other of R^(1a) and R^(1b) independently is a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments one of R^(1a) and R^(1b) independently is a hydrogen, hydrocarbyl or halogen atom, and the other of R^(1a) and R^(1b) independently is a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments each of R^(1a) and R^(1b) independently is a hydrogen, hydrocarbyl or halogen atom. In some embodiments at least one of R^(1a) and R^(1b) is hydrocarbyl. In some embodiments R^(1a) and R^(1b) is halogen.

In some embodiments one of R^(2a) and R^(2b) independently is a hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom, and the other of R^(2a) and R^(2b) independently is a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments one of R^(2a) and R^(2b) independently is a hydrogen, hydrocarbyl or halogen atom, and the other of R^(2a) and R^(2b) independently is a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments each of R^(2a) and R^(2b) independently is a hydrogen, hydrocarbyl or halogen atom. In some embodiments at least one of R^(2a) and R^(2b) is hydrocarbyl. In some embodiments at least one of R^(2a) and R^(2b) is a halogen atom.

Certain combinations of R^(1a), R^(1b), R^(2a), and R^(2b) are preferred. In some embodiments R^(1a) is a hydrogen atom; R^(1b) is a hydrocarbyl, heterohydrocarbyl, or halogen atom; R^(2a) independently is a hydrocarbyl, heterohydrocarbyl, or halogen atom; and R^(2b) independently is a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments R^(1b) independently is hydrocarbyl or a halogen atom.

In some embodiments each of R^(1a) and R^(1b) is a hydrogen atom; and at least one, and preferably each of R^(2a) and R^(2b) independently is a hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments at least one and preferably each of the R^(2a) and R^(2b) independently is hydrocarbyl or a halogen atom.

In some embodiments at least three of R^(1a), R^(1b), R^(2a), and R^(2b) independently is a hydrogen, hydrocarbyl, heterohydrocarbyl, or a halogen atom; and the remaining one of R^(1a), R^(1b), R^(2a), and R^(2b) independently is a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or a halogen atom. In some embodiments at least three and in other embodiments each of R^(1a), R^(1b), R^(2a), and R^(2b) independently is a hydrocarbyl or a halogen atom.

Certain combinations of R^(2a), R^(2b), R^(3a), and R^(3b) are preferred. In some embodiments R^(2a) a is a hydrogen atom; R^(2b) is a hydrocarbyl, heterohydrocarbyl, or halogen atom; R^(3a) independently is hydrogen, a hydrocarbyl, heterohydrocarbyl, or a halogen atom; and R^(3b) independently is a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or a halogen atom. In some embodiments R^(2b) independently is hydrocarbyl or halogen atom.

Certain combinations of R^(1a), R^(1b), R^(2a), R^(2b), R^(3a), and R^(3b) are more preferred. In some embodiments R^(2a) and R^(2b) are each hydrogen atom and R^(1a), R^(1b), R^(3a), and R^(3b) independently is hydrocarbyl, heterohydrocarbyl, or halogen atom; and more preferably R^(2a) and R^(2b) are each hydrogen atom and each of R^(1a) and R^(1b) independently is (C₁-C₆)hydrocarbyl, (C₁-C₅)heterohydrocarbyl, fluorine atom, or chlorine atom, and each of R^(3a), and R^(3b) independently is (C₁-C₁₂)hydrocarbyl, (C₁-C₁₁)heterohydrocarbyl, fluorine atom, chlorine atom, or bromine atom. In some embodiments R^(1a) and R^(1b) are each hydrogen atom; each of R^(2a) and R^(2b) independently is (C₁-C₈)hydrocarbyl, (C₁-C₇)heterohydrocarbyl, fluorine atom, chlorine atom, or bromine atom; and each of R^(3a), and R^(3b) independently is (C₁-C₁₂)hydrocarbyl, (C₁-C₁₁)heterohydrocarbyl, fluorine atom, chlorine atom, or bromine atom.

Preferably each hydrocarbyl, whenever used to define R^(1a), R^(1b), R^(2a), R^(2b), R^(3a), or R^(3b), independently is an alkyl or cycloalkyl. Preferably the alkyl is (C₁-C₁₂)alkyl, more preferably (C₁-C₈)alkyl, still more preferably (C₁-C₆)alkyl, and even more preferably (C₁-C₄)alkyl. Preferably the cycloalkyl is (C₃-C₆)cycloalkyl, and more preferably (C₃-C₄)cycloalkyl. Preferably the (C₃-C₄)cycloalkyl is cyclopropyl. Preferably the (C₁-C₄)alkyl is methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, or 1,1-dimethylethyl, and more preferably methyl, ethyl, 2-propyl, or 1,1-dimethylethyl. In some embodiments the (C₁-C₄)alkyl is ethyl, 2-propyl, or 1,1-dimethylethyl. Preferably each halogen atom, whenever used to define R^(1a), R^(1b), R^(2a), R^(2b), R^(3a), and R^(3b)b, independently is a fluorine atom or chlorine atom.

In some embodiments each of R^(1a), R^(1b), R^(3a), and R^(3b) independently is methyl; ethyl; 2-propyl; 1,1-dimethylethyl; mono-, di-, or trifluoromethyl; methoxy; ethoxy; 1-methylethoxy; mono-, di-, or trifluoromethoxy; halogen atom; cyano; nitro; dimethylamino; aziridin-1-yl; or cyclopropyl. In some embodiments at least one, and in some embodiments each of R^(2a) and R^(2b) is a hydrogen atom and each of R^(1a), R^(1b), R^(3a), and R^(3b) independently is methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 1,1-dimethylethyl; cyano; dimethylamino; methoxy; trifluoromethyl; bromine atom; fluorine atom; or chlorine atom.

In some embodiments of the metal-ligand complex of formula (I) each of R^(1a) and R^(1b) is a hydrogen atom and at least one, and in some embodiments each of R^(2a), R^(2b), R^(3a), and R^(3b) independently is methyl; ethyl; 2-propyl; 1,1-dimethylethyl; mono-, di-, or trifluoromethyl; methoxy; ethoxy; 1-methylethoxy; mono-, di-, or trifluoromethoxy; halogen atom; cyano; nitro; dimethylamino; aziridin-1-yl; or cyclopropyl. In some embodiments at least one, and in some embodiments each of R^(1a) and R^(1b) is a hydrogen atom and each of R^(2a), R^(2b), R^(3a), and R^(3b) independently is methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 1,1-dimethylethyl; cyano; dimethylamino; methoxy; trifluoromethyl; bromine atom; fluorine atom; or chlorine atom.

In some embodiments the metal-ligand complex of formula (I) one of R^(1a) and R^(1b) is methyl; the other of R^(1a) and R^(1b) is as in any one of the preferred embodiments described herein. More preferably in some of such embodiments each of R^(2a) and R^(2b) is a hydrogen atom and each of R^(3a) and R^(3b) independently is as in any one of the preferred embodiments described herein.

In some embodiments the metal-ligand complex of formula (I) at least one, and more preferably each of R^(1a) and R^(1b) independently is ethyl; 2-propyl; mono-, di-, or trifluoromethyl; methoxy; ethoxy; 1-methylethoxy; mono-, di-, or trifluoromethoxy; halogen atom; cyano; nitro; dimethylamino; aziridin-1-yl; or cyclopropyl. More preferably in such embodiments at least one, and more preferably each of R^(2a) and R^(2b) is a hydrogen atom and each of R^(3a) and R^(3b) independently is as in any one of the preferred embodiments described herein. In some of such embodiments preferably at least one, and more preferably each of R^(1a) and R^(1b), is a halogen atom or (C₁-C₆)alkyl, and still more preferably a (C₂-C₄)alkyl, fluorine or chlorine atom. In some embodiments at least one, and preferably each of R^(1a) and R^(1b), is the fluorine atom. In some embodiments at least one, and preferably each of R^(1a) and R^(1b), is the chlorine atom. In some embodiments at least one, and preferably each of R^(1a) and R^(1b), is (C₁-C₄)alkyl, and more preferably methyl. In general any combination of R^(1a) and R^(1b), R^(2a) and R^(2b), and R^(3a) and R^(3b) may be made, within the selections provided, enabled, or exemplified.

In some embodiments of the metal-ligand complex of formula (I) or the ligand of formula (Q), at least one of R^(1a), R^(1b), R^(3a), R^(3b), R^(7c), and R^(7d) is not methyl. In some embodiments of the metal-ligand complex of formula (I) at least one of R^(7c), R^(7d), R^(3a), and R^(3b) is not methyl.

Certain R^(4a) and R^(4b) are preferred. In some embodiments each of R^(4a) and R^(4b) is a hydrogen atom. In some embodiments at least one and in some embodiments each of R^(4a) and R^(4b) independently is as defined previously for R^(1a) and R^(1b), respectively. When R^(4a) or R^(4b) independently is as defined previously for R^(1a) or R^(1b), respectively, or both, R^(4a) and R^(1a) independently may be the same or different and R^(4b) and R^(1b) independently may be the same or different. In some embodiments at least one, and in some embodiments each of R^(4a) and R^(4b) independently is methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 1,1-dimethylethyl; cyano; dimethylamino; methoxy; trifluoromethyl; bromine atom; fluorine atom; or chlorine atom.

Certain R^(5c) and R^(5d) are preferred. In some embodiments R^(5c) and R^(5d) are the same as each other. In some embodiments R^(5c) and R^(5d) are different from each other.

In some embodiments at least one, and more preferably each of R^(5c) and R^(5d) independently is (C₆-C₄₀)aryl. Preferably the (C₆-C₄₀)aryl is a (C₆-C₁₈)aryl and more preferably (C₆-C₁₂)aryl. In some embodiments the (C₆-C₄₀)aryl is a substituted phenyl and preferably a 2,4-disubstituted phenyl wherein each substituent is R^(S), 2,5-disubstituted phenyl wherein each substituent is R^(S); or 2,6-disubstituted phenyl wherein each substituent is R^(S); and more preferably wherein each R^(S) independently is phenyl, methyl, ethyl, isopropyl, or tertiary-butyl, and still more preferably 2,6-dimethylphenyl or 2,6-diisopropylphenyl. In some embodiments the (C₆-C₄₀)aryl is a 3,5-disubstituted phenyl wherein each substituent is R^(S), and more preferably wherein each R^(S) independently is phenyl, methyl, ethyl isopropyl, or tertiary-butyl, and still more preferably 3,5-di(tertiary-butyl)phenyl or 3,5-diphenylphenyl. In some embodiments the (C₆-C₄₀)aryl is a 2,4,6-trisubstituted phenyl wherein each substituent is R^(S), and more preferably wherein each R^(S) independently is phenyl, methyl, isopropyl, or tertiary-butyl; In some embodiments the (C₆-C₄₀)aryl is a naphthyl or substituted naphthyl wherein each substituent is R^(S), and more preferably wherein each R^(S) independently is phenyl, methyl, ethyl, isopropyl, or tertiary-butyl, and still more preferably 1-naphthyl, 2-methyl-1-naphthyl, or 2-naphthyl. In some embodiments the (C₆-C₄₀)aryl is a 1,2,3,4-tetrahydronaphthyl, and more preferably 1,2,3,4-tetrahydronaphth-5-yl or 1,2,3,4-tetrahydronaphth-6-yl. In some embodiments the (C₆-C₄₀)aryl is an anthracenyl, and more preferably anthracen-9-yl. In some embodiments the (C₆-C₄₀)aryl is a 1,2,3,4-tetrahydro-anthracenyl, and more preferably 1,2,3,4-tetrahydroanthracen-9-yl. In some embodiments the (C₆-C₄₀)aryl is a 1,2,3,4,5,6,7,8-octahydroanthracenyl, and more preferably 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl. In some embodiments the (C₆-C₄₀)aryl is a phenanthrenyl, and more preferably a phenanthren-9-yl. In some embodiments the (C₆-C₄₀)aryl is a 1,2,3,4,5,6,7,8-octahydrophenanthrenyl, and more preferably 1,2,3,4,5,6,7,8-octahydro-phenanthren-9-yl. As mentioned before, each of the aforementioned (C₆-C₄₀)aryl independently is unsubstituted or substituted by one or more substituents R^(S). In some embodiments the (C₆-C₄₀)aryl is unsubstituted. Preferred unsubstituted (C₆-C₄₀)aryl is unsubstituted inden-6-yl; 2,3-dihydro-1H-inden-6-yl; naphthalene-2-yl; or 1,2,3,4-tetrahydronaphthalen-6-yl; and more preferably unsubstituted naphthalen-1-yl; 1,2,3,4-tetrahydronaphthalen-5-yl; anthracen-9-yl; 1,2,3,4-tetrahydroanthracen-9-yl; or 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl. As mentioned for (C₆-C₄₀)aryl hereinabove, each of the aforementioned (C₆-C₄₀)aryl independently is unsubstituted or substituted by one or more substituents R^(S). In some embodiments the (C₆-C₄₀)aryl is substituted by from 1 to 4 R^(S), wherein R^(S) is as described previously. Preferably there are 1 or 2 R^(S) substituents in each substituted (C₆-C₄₀), and more preferably 2 R^(S) substituents in each substituted phenyl. Preferably each R^(S) of the substituted (C₆-C₄₀)aryl of R^(5c) and R^(5d) independently is an unsubstituted (C₃-C₁₀)hydrocarbyl, more preferably an unsubstituted (C₄-C₈)hydrocarbyl, still more preferably phenyl or an unsubstituted (C₄-C₁₀)alkyl, and even more preferably an unsubstituted tertiary (C₄-C₈)alkyl (e.g., tertiary-butyl or tertiary-octyl (i.e., 1,1-dimethylhexyl)). Examples of preferred substituted (C₆-C₄₀)aryl are a 2,6-disubstituted-phenyl having same substituent R^(S) (e.g., 2,6-dimethylphenyl; 2,6-diethylphenyl; 2,6-bis(1-methylethyl)phenyl; and 2,6-diphenyl-phenyl); a 3,5-disubstituted-phenyl having same substituent R^(S) (e.g., 3,5-dimethylphenyl; 3,5-bis(trifluoromethyl)phenyl; 3,5-bis(1-methylethyl)phenyl; and 3,5-bis(1,1-dimethylethyl)phenyl; and 3,5-diphenyl-phenyl); 2,4,6-trisubstituted-phenyl having same substituent R^(S) (e.g., 2,4,6-trimethylphenyl; and 2,4,6-tris(1-methylethyl)phenyl); 1-methyl-2,3-dihydro-1H-inden-6-yl; 1,1-dimethyl-2,3-dihydro-1H-inden-6-yl; 1-methyl-1,2,3,4-tetrahydro-naphthalen-5-yl; and 1,1-dimethyl-1,2,3,4-tetrahydronaphthalen-5-yl.

In some embodiments at least one, and more preferably each of R^(5c) and R^(5d) independently is heteroaryl. Preferably the heteroaryl has at least one nitrogen atom-containing aromatic ring. More preferably the heteroaryl is a pyridinyl, indolyl, indolinyl, quinolinyl, 1,2,3,4-tetrahydroquinolinyl, isoquinolinyl, 1,2,3,4-tetrahydroisoquinolinyl, carbazolyl, 1,2,3,4-tetrahydrocarbazolyl, or 1,2,3,4,5,6,7,8-octahydrocarbazolyl. In some embodiments the heteroaryl is carbazolyl or a substituted carbazolyl, preferably a 2,7-disubstituted carbazolyl or 3,6-disubstituted carbazolyl, and more preferably 2,7-disubstituted 9H-carbazol-9-yl or 3,6-disubstituted 9H-carbazol-9-yl, wherein each substituent is R^(S), more preferably wherein each R^(S) independently is phenyl, methyl, ethyl, isopropyl, or tertiary-butyl, still more preferably 3,6-di(tertiary-butyl)-carbazolyl, 3,6-di(tertiary-octyl)-carbazolyl, 3,6-diphenylcarbazolyl, or 3,6-bis(2,4,6-trimethylphenyl)-carbazolyl, and more preferably 3,6-di(tertiary-butyl)-carbazol-9-yl, 3,6-di(tertiary-octyl)-carbazol-9-yl, 3,6-diphenylcarbazol-9-yl, or 3,6-bis(2,4,6-trimethylphenyl)-carbazol-9-yl. Examples of 2,7-disubstituted carbazolyl are the foregoing 3,6-disubstituted carbazolyl where the 3,6-substituents are moved to 2,7-positions, respectively. Tertiary-octyl is 1,1-dimethylhexyl. In some embodiments the heteroaryl is 1,2,3,4-tetrahydrocarbazolyl, preferably a 1,2,3,4-tetrahydrocarbazol-9-yl. As mentioned before for heteroaryl, each of the aforementioned heteroaryl independently is unsubstituted or substituted by one or more substituents R^(S). Preferably each of the indolyl, indolinyl, and tetrahydro- and octahydro-containing heteroaryl is bonded via its ring nitrogen atom to the phenyl rings bearing R^(5c) or R^(5d) in formula (I). In some embodiments the heteroaryl is unsubstituted. Preferred unsubstituted heteroaryl is unsubstituted quinolin-4-yl, quinolin-5-yl, or quinolin-8-yl, (the quinolinyl N being at position 1); 1,2,3,4-tetrahydroquinolin-1-yl (the tetrahydroquinolinyl N being at position 1); isoquinolin-1-yl, isoquinolin-4-yl, isoquinolin-5-yl, or isoquinolin-8-yl (the isoquinolinyl N being at position 2); 1,2,3,4-tetrahydroisoquinolin-2-yl (the tetrahydroisoquinolinyl N being at position 2); 1H-indol-1-yl (the indolyl N being at position 1); 1H-indolin-1-yl (the indolinyl N being at position 1); 9H-carbazol-9-yl (the carbazolyl N being at position 9), which may also be named as a dibenzo-1H-pyrrole-1-yl; 1,2,3,4-tetrahydrocarbazolyl-9-yl (the tetrahydrocarbazolyl N being at position 9); or 1,2,3,4,5,6,7,8-octahydrocarbazolyl-9-yl (the octahydrocarbazolyl N being at position 9). In some embodiments the heteroaryl is substituted by from 1 to 4 R^(S). Preferably there are 1 or 2 R^(S) substituents in each substituted heteroaryl. Preferably each R^(S) of the substituted heteroaryl of R^(5c) and R^(5d) independently is an unsubstituted (C₃-C₁₀)hydrocarbyl, more preferably an unsubstituted (C₄-C₈)hydrocarbyl, still more preferably phenyl or an unsubstituted (C₄-C₁₀)alkyl, and even more preferably an unsubstituted tertiary (C₄-C₈)alkyl (e.g., tertiary-butyl or tertiary-octyl (i.e., 1,1-dimethylhexyl)). Preferably the substituted heteroaryl is a 2,7-disubstituted quinolin-4-yl, 2,7-disubstituted quinolin-5-yl, or 3,6-disubstituted quinolin-8-yl; 3,6-disubstituted 1,2,3,4-tetrahydroquinolin-1-yl; 4-monosubstituted isoquinolin-5-yl; 2-monosubstituted 1,2,3,4-tetrahydroisoquinolin-2-yl; 3-monosubstituted 1H-indol-1-yl; 3-monosubstituted 1H-indolin-1-yl; 2,7-disubstituted 9H-carbazol-9-yl; 3,6-disubstituted 9H-carbazol-9-yl; 3,6-disubstituted 1,2,3,4-tetrahydrocarbazolyl-9-yl; or 3,6-disubstituted 1,2,3,4,5,6,7,8-octahydrocarbazolyl-9-yl. Examples of preferred substituted heteroaryl are 4,6-bis(1,1-dimethylethyl)pyridine-2-yl; 4,6-diphenylpyridin-2-yl; 3-phenyl-1H-indol-1-yl; 3-(1,1-dimethylethyl)-1H-indol-1-yl; 3,6-diphenyl-9H-carbazol-9-yl; 3,6-bis[2′,4′,6′-tris(1,1-dimethylphenyl)]-9H-carbazol-9-yl; and more preferably each of R^(5c) and R^(5d) d is 3,6-bis(1,1-dimethylethyl)-9H-carbazol-9-yl. The term “tertiary butyl” means 1,1-dimethylethyl. More preferably R^(5c) and R^(5d) are defined as in any one of the Examples described later.

In some embodiments the metal-ligand complex of formula (I) each Z is O, each of R^(2a) and R^(2b) s a hydrogen atom, and each of R^(5c) and R^(5d) independently is the heteroaryl. More preferred in such embodiments is a metal-ligand complex of any one of formulas (Ia) to (Ie):

-   wherein M, X, R^(1a), R^(1b), R^(3a), R^(3b), R^(7c), R^(7d), and L     are as defined previously and each R⁵⁵ and R⁶⁵ is as defined     previously. Preferably each R⁵⁵ and R⁶⁵ independently is a hydrogen     atom or an unsubstituted (C₁-C₁₂)alkyl.

In some embodiments the metal-ligand complex of formula (I) each Z is O, each of R^(1a), and R^(1b) is a hydrogen atom, and each of R^(5c) and R^(5d) independently is the heteroaryl. More preferred in such embodiments is a metal-ligand complex of any one of formulas (If) to (Ij):

-   wherein M, X, R^(2a), R^(2b), R^(3a), R^(3b), R^(7c), R^(7d), and L     are as defined previously and each R⁵⁵ and R⁶⁵ is as defined     previously. Preferably each R⁵⁵ and R⁶⁵ independently is a hydrogen     atom or an unsubstituted (C₁-C₁₂)alkyl.

In some embodiments the metal-ligand complex of formula (I) each Z is O, each of R^(2a) and R^(2b) is a hydrogen atom, and each of R^(5c) and R^(5d) independently is the (C₆-C₄₀)aryl. More preferred in such embodiments is a metal-ligand complex of any one of formulas (Ik) to (Io):

-   wherein M, X, R^(1a), R^(1b), R^(3a), R^(3b)R^(7c), R^(7d), and L     are as defined previously and each R⁵⁵ and R⁶⁵ is as defined     previously. Preferably each R⁵⁵ and R⁶⁵ independently is a hydrogen     atom or an unsubstituted (C₁-C₁₂)alkyl.

In some embodiments the metal-ligand complex of formula (I) each Z is O, each of R^(1a), R^(2b), R^(2a) and R^(2b) is a hydrogen atom, and each of R^(5c) and R^(5d) independently is the (C₆-C₄₀)aryl or (C₆-C₄₀)heteroaryl. More preferred in such embodiments is a metal-ligand complex of any one of formulas (Ip) to (It):

-   wherein M, X, R^(3a), R^(3b), R^(7c), R^(7d), and L are as defined     previously and each R⁵⁵ and R⁶⁵ is as defined previously. Preferably     each R⁵⁵ and R⁶⁵ independently is a hydrogen atom or an     unsubstituted (C₁-C₁₂)alkyl.

As mentioned above for the metal-ligand complex of any one of formulas (Ia) to (Io), the M, X, L, R^(1a), R^(2a), R^(3a), R^(1b), R^(2b), R^(3b), R^(7c), and R^(7d), as the case may be, are as defined for the same of formula (I) (i.e., as M, X, L, R^(1a), R^(2a), R^(3a), R^(1b), R^(2b), R^(3b), R^(7c), and R^(7d) of formula (I)). Preferably M is hafnium or zirconium, and more preferably hafnium. Preferably each X is a monodentate ligand. In some embodiments of the metal-ligand complex of any one of formulas (Ia) to (Io), n is 2 or 3 and at least two X independently are monoanionic monodentate ligands and a third X, if present, is a neutral monodentate ligand. In some embodiments L is —CH₂CH₂—, —CH(CH₃)CH(CH₃)—, —CH₂C(CH₃)₂—, or —CH₂Si(CH₃)₂—. In some embodiments each of R^(1a), R^(2a), R^(3a), R^(1b), R^(2b), R^(3b) independently is hydrogen atom, methyl; ethyl; 2-propyl; 1,1-dimethylethyl; mono-, di-, or trifluoromethyl; methoxy; ethoxy; 1-methylethoxy; mono-, di-, or trifluoromethoxy; halogen atom; cyano; nitro; dimethylamino; aziridin-1-yl; or cyclopropyl, wherein at least one of R^(1a), R^(2a), and R^(3a) independently is not the hydrogen atom and at least one of R^(1b), R^(2b), and R^(3b) independently is not the hydrogen atom. In some embodiments each of R^(7c) and R^(7d) independently is (C₄-C₈)alkyl.

The invention process employs catalytic amounts of the invention catalyst. When more than one catalyst is employed, each catalyst independently will be in a catalytic amount. The term “catalytic amount” means less than a stoichiometric quantity based on number of moles of a product-limiting stoichiometric reactant employed in the invention process. The catalytic amount is also equal to or greater than a minimum amount of the metal-ligand complex of formula (I) that is necessary for at least some product of the catalyzed reaction to be formed and detected (e.g., by mass spectrometry). The minimum catalytic amount preferably is 0.0001 mole percent of the number of moles of a product-limiting stoichiometric reactant. In the invention process the product-limiting stoichiometric reactant for the invention catalyst typically will be ethylene. Preferably, the catalytic amount of the metal-ligand complex of formula (I) used to prepare the invention catalyst is from 0.001 mol % to 50 mol % of the moles of ethylene or (C₃-C₄₀)α-olefin, whichever is lower. More preferably, the catalytic amount of the metal-ligand complex of formula (I) is at least 0.01 mol %, still more preferably at least 0.05 mol %, and even more preferably at least 0.1 mol %. Also more preferably, the catalytic amount of the metal-ligand complex of formula (I) is 40 mol % or less, and still more preferably 35 mol % or less.

Preferably the catalyst has a minimum catalyst efficiency or higher. The catalyst efficiency is calculated by dividing the number of grams of polyethylene or poly(co-ethylene-α-olefin) prepared by the number of grams of metal(M) in ingredient (a) (i.e., M in metal-ligand complex of formula (I)) employed (i.e., catalyst efficiency=g PE prepared/g M in metal-ligand complex of formula (I) employed). Preferably when the catalyst efficiency is determined employing ethylene and 1-octene at a polymerization reaction temperature of 170° C. and 0.10 micromole (μmol) of the metal-ligand complex of formula (I), 0.12 μmol of the activating co-catalyst, bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate ([HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄], abbreviated as BOMATPB), and 1.0 μmol of another activating co-catalyst that is a triisobutylaluminum-modified methylalumoxane-3A (MMAO-3A), hydrogen gas, and a mixed alkanes solvent, the catalyst efficiency is greater than 740,000, more preferably greater than 960,000, still more preferably greater than 1,480,000, and even more preferably greater than 1,900,000. Preferably when the catalyst efficiency is determined employing ethylene and 1-octene as described later at a polymerization reaction temperature of 170° C. and 0.08 μmol of the metal-ligand complex of formula (I), 0.096 μmol of the BOMATPB, and 0.8 μmol of MMAO-3A, the catalyst efficiency is greater than 1,1,480,000. Preferably when the catalyst efficiency is determined employing ethylene and 1-octene as described later at a polymerization reaction temperature of 170° C. and 0.075 μmol of the metal-ligand complex of formula (I), 0.09 μmol of the BOMATPB, and 0.75 μmol of MMAO-3A, the catalyst efficiency is greater than 970,000, more preferably greater than 1,060,000, and still more preferably greater than 1,090,000. Preferably when the catalyst efficiency is determined employing ethylene and 1-octene as described later at a polymerization reaction temperature of 170° C. and 0.05 μmol of the metal-ligand complex of formula (I), 0.06 μmol of the BOMATPB, and 0.5 μmol of MMAO-3A, the catalyst efficiency is greater than 920,000, more preferably greater than 940,000, and still more preferably greater than 2,900,000. More preferably the catalyst efficiency is as defined as in any one of the Examples described later.

In some embodiments, the catalyst, catalyst system or composition, or both further comprises one or more solvents, diluents, or a combination thereof. In other embodiments, such may further comprise a dispersant, e.g., an elastomer, preferably dissolved in the diluent. In these embodiments, the catalyst is preferably homogeneous.

The invention further requires a cocatalyst for activation of the metal-ligand complex. Where there are two or more such cocatalysts, they can be activated by the same or different. Many cocatalysts and activating techniques have been previously taught with respect to different metal-ligand complexes in the following U.S. Patents (US): U.S. Pat. No. 5,064,802; U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,296,433; U.S. Pat. No. 5,321,106; U.S. Pat. No. 5,350,723; U.S. Pat. No. 5,425,872; U.S. Pat. No. 5,625,087; U.S. Pat. No. 5,721,185; U.S. Pat. No. 5,783,512; U.S. Pat. No. 5,883,204; U.S. Pat. No. 5,919,983; U.S. Pat. No. 6,696,379; and U.S. Pat. No. 7,163,907. Preferred cocatalysts (activating co-catalysts) for use herein include alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activating technique is, for example, bulk electrolysis, which is well known to those skilled in the art. Combinations of one or more of the foregoing cocatalysts and techniques are also contemplated. The term “alkyl aluminum” means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum. Preferably the alkyl of the foregoing alkyl-aluminums is from 1 to 10 carbon atoms. Triethylaluminum is more preferred. Aluminoxanes and their preparations are known at, for example, U.S. Pat. No. 6,103,657. Examples of preferred polymeric or oligomeric alumoxanes are methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane. Other preferred cocatalysts are tri((C₆-C₁₈)aryl)boron compounds and halogenated (including perhalogenated) derivatives thereof, (e.g., tris(pentafluorophenyl)borane, trityl tetrafluoroborate, or, more preferably bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane ([HNMe(C₁₈H₃₇)₂]—[B(C₆F₅)₄], abbreviated as BOMATPB)). In some embodiments at least two of the cocatalysts are used in combination with each other.

The ratio of total number of moles of one or more metal-ligand complexes of formula (I) to total number of moles of one or more of the activating co-catalysts is from 1:10,000 to 100:1. Preferably, the ratio is at least 1:5000, more preferably at least 1:1000; and 10:1 or less, more preferably 1:1 or less. When an alumoxane alone is used as the activating co-catalyst, preferably the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the metal-ligand complex of formula (I). When tris(pentafluorophenyl)borane alone is used as the activating co-catalyst, preferably the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more metal-ligand complexes of formula (I) may vary from 0.5:1 to 10:1, more preferably from 1:1 to 6:1, and still more preferably from 1:1 to 5:1. The remaining activating co-catalysts are generally employed in mole quantities that are approximately equal to the total mole quantities of one or more metal-ligand complexes of formula (I).

In certain circumstances the comonomer incorporation index may be determined directly, for example, by the use of NMR spectroscopic techniques described previously or by IR spectroscopy. If NMR or IR spectroscopic techniques cannot be used, then any difference in comonomer incorporation is indirectly determined. For polymers formed from multiple monomers this indirect determination may be accomplished by various techniques based on monomer reactivities.

Olefin polymerizing conditions employed herein independently refer to reaction conditions such as solvent(s), atmosphere(s), temperature(s), pressure(s), time(s), and the like that are preferred for producing, after 15 minutes reaction time, at least a 10 percent (%), more preferably at least 20%, and still more preferably at least 30% reaction yield of the poly-α-olefin or poly(co-ethylene-α-olefin) having a molecular weight less than 2500 Da from the invention process. Preferably, the process is independently run under an inert atmosphere (e.g., under an inert gas consisting essentially of, for example, nitrogen gas, argon gas, helium gas, or a mixture of any two or more thereof). Other atmospheres are contemplated, however, and these include sacrificial olefin in the form of a gas and hydrogen gas (e.g., as a polymerization termination agent). In some aspects, the process may be run neat, without solvent and with or without additional ingredients (e.g., catalyst stabilizer such as triphenylphosphine). In still other aspects, it may be run with a solvent or mixture of two or more solvents, e.g., an aprotic solvent. Preferably, the neat process or solvent-based process is run at a temperature of the neat mixture or solvent-containing mixture of at least 100° C. A convenient temperature is from about 120° C., preferably 140° C. to about 250° C., preferably 230° C., more preferably 190° C. (e.g., at 150° C. or 170° C. or 190° C.). Preferably the process is run under a pressure from about 0.9 atmospheres (atm) to about 10 atm (i.e., from about 91 kiloPascals (kPa) to about 1010 kPa). More preferably, the pressure is about 1 atm (i.e., about 101 kPa).

In some embodiments, polymerizable olefins useful in the invention process are (C₂-C₄₀)hydrocarbons consisting of carbon and hydrogen atoms and containing at least 1, and preferably no more than 3, and more preferably no more than 2, carbon-carbon double bonds. In some embodiments, from 1 to 4 hydrogen atoms of the (C₂-C₄₀)hydrocarbons are replaced, each by a halogen atom, preferably fluoro or chloro to give halogen atom-substituted (C₂-C₄₀)hydrocarbons as the useful polymerizable olefins. The (C₂-C₄₀)hydrocarbons (not halogen atom-substituted) are preferred. Preferred polymerizable olefins (i.e., olefin monomers) useful for making the polyolefins are ethylene and polymerizable (C₃-C₄₀)olefins. The (C₃-C₄₀)olefins include an α-olefin, a cyclic olefin, styrene, and a cyclic or acyclic diene. In some embodiments at least one of the other polymerizable olefin is the α-olefin, and more preferably a (C₃-C₄₀)α-olefin. In some embodiments the (C₃-C₄₀)α-olefin is a (C₄-C₄₀)α-olefin, more preferably a (C₆-C₄₀)α-olefin, still more preferably a (C₇-C₄₀)α-olefin, and even more preferably a (C₈-C₄₀)α-olefin. Preferably, the α-olefin comprises the (C₃-C₄₀)α-olefin, more preferably a branched chain (C₃-C₄₀)α-olefin, still more preferably a linear-chain (C₃-C₄₀)α-olefin, even more preferably a linear chain (C₃-C₄₀)α-olefin of formula (A): CH₂═CH₂—(CH₂)_(Z)CH₃ (A), wherein z is an integer of from 0 to 40, and yet even more preferably a linear-chain (C₃-C₄₀)α-olefin that is 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-hepta-decene, 1-octadecene, or a linear-chain (C₂₀-C₂₄)α-olefin. Preferably the cyclic olefin is a (C₃-C₄₀)cyclic olefin. Preferably, the cyclic or acyclic diene is a (C₄-C₄₀)diene, preferably an acyclic diene, more preferably an acyclic conjugated (C₄-C₄₀)diene, more preferably an acyclic 1,3-conjugated (C₄-C₄₀)diene, and still more preferably 1,3-butadiene.

Polyolefins that can be made by the invention process include, for example, interpolymers that comprise residuals of ethylene and one or more polymerizable (C₃-C₄₀)olefins. Preferred interpolymers are those prepared by co-polymerizing a mixture of two or more polymerizable olefins such as, for example, ethylene/propylene, ethylene/1-butene, ethylene/1-pentene, ethylene/1-hexene, ethylene/4-methyl-1-pentene, ethylene/1-octene, ethylene/styrene, ethylene/propylene/butadiene and other EPDM terpolymers. Preferably, the polyolefin is an ethylene homopolymer (e.g., a high density polyethylene), an ethylene/α-olefin interpolymer (i.e., poly(co-ethylene-α-olefin), such as, for example, a poly(ethylene 1-octene)), or an ethylene/α-olefin/diene interpolymer (i.e., a poly(ethylene α-olefin diene) terpolymer such as, for example, a poly(ethylene 1-octene 1,3-butadiene).

Preferably, the mole ratio of (moles of (C₃-C₄₀)α-olefin)/(moles of ethylene) is 0.1 or higher, more preferably 0.30 or higher, still more preferably 0.50 or higher, and even more preferably 0.75 or higher (e.g., 1.0 or higher).

In another embodiment, the present invention is a polyolefin, preferably the polyethylene (e.g., in an isolated form or as part of an intermediate mixture with the α-olefin) prepared by the invention process.

The inventive process may be run in one reactor or in multiple reactors. For example, single reactor, multiple catalyst processes are useful in the present invention. In one embodiment, two or more catalysts are introduced into a single reactor under the olefin polymerization conditions, wherein at least the first one of the catalysts is a catalyst of the group specified herein and each catalyst inherently produces a mixture or blend of different polyolefin copolymers. The terms “mixture” and “blend” as applied to the polyolefin copolymers are synonymous. Use of different catalysts within the invention may result in similar or different comonomer incorporation, but products within the invention will fall into a weight average molecular weight range of less than 2500 Da, preferably less than 1500 Da. Variation of the ratio of two or more catalysts within a single reactor will vary the product ratio, and knowledge of such is within that of those skilled in the art. See also, U.S. Pat. No. 6,924,342. The invention catalysts are compatible with other olefin polymerization catalysts, including Ziegler/Natta catalysts. Due to this compatibility, an additional catalyst included in one reaction may comprise a metallocene or other π-bonded ligand group containing metal-ligand complex (including constrained geometry metal-ligand complexes), or a polyvalent heteroatom ligand group containing metal-ligand complex, especially polyvalent pyridylamine or imidizolylamine based complexes and tetradentate oxygen-ligated biphenylphenol based Group 4 metal-ligand complexes. Preferably, the invention catalyst is prepared from, and the invention process employs, three or fewer, more preferably two, and still more preferably one metal-ligand complex of formula (I) per reactor. Further discussion of such may be found in co-pending U.S. Patent Publication No. 2011/0282018 A1, filed May 11, 2011.

In some embodiments a preferred invention process can achieve a minimum molecular weight distribution or polydispersity index (PDI) of the polyolefin product produced thereby. In some embodiments the PDI is greater than 2.4, in other embodiments the PDI is greater than 4.0, in other embodiments the PDI is greater than 6.0, and in still other embodiments the PDI is greater than 8.0. In some embodiments the PDI is less than 11.

In some embodiments a preferred invention process can achieve a productivity ratio of weight of polyolefin produced per weight of ethylene employed, as determined employing ethylene and 1-octene as described later at a polymerization reaction temperature of 170° C., wherein the productivity ratio of the polyolefin produced to ethylene employed is greater than 1.00, preferably greater than 1.10, more preferably greater than 1.40, and still more preferably greater than 2.50.

EXAMPLES General Analysis Procedure

Gel permeation chromatography (GPC): Determine weight average molecular weight (M_(w)) and polydispersity index: Determine M_(w) and ratio of M_(w)/M_(n) (polydispersity index or PDI) using a Polymer Labs™ 210 high temperature gel permeation chromatograph. Prepare samples using 13 mg of polyethylene polymer that is diluted with 16 mL of 1,2,4-trichlorobenzene (stabilized with butylated hydroxy toluene (BHT)), heat and shake at 160° C. for 2 hours.

Determining melting and crystallization temperatures and heat of fusion by Differential Scanning Calorimetry (DSC; DSC 2910, TA Instruments, Inc.)): First heat samples from room temperature to 180° C. at a heating rate of 10° C. per minute. After being held at this temperature for 2 to 4 minutes, cool the samples to −40° C. at a cooling rate of 10° C. per minute; hold the sample at the cold temperature for 2 to 4 minutes, and then heat the sample to 160° C.

Abbreviations (meanings): r.t. (room temperature); g (gram(s)); mL (milliliter(s)); ° C. (degrees Celsius); mmol (millimole(s)); MHz (MegaHertz); Hz (Hertz).

Synthesis Procedures for Metal-Ligand Complexes

Step 1: Preparation of 3,6-bis(1,1-dimethylethyl)-9H-carbazole

To a 500 mL three-necked round bottom flask equipped with an overhead stirrer, nitrogen gas bubbler, and an addition funnel are added 20.02 g (120.8 mmol) of carbazole, 49.82 g (365.5 mmol) of ZnCl₂, and 300 mL of nitromethane at r.t. To the resulting dark brown slurry is added 49.82 g (365.5 mmol) of 2-chloro-2-methylpropane dropwise from the addition funnel over a period of 2.5 hours. After completing the addition, the resulting slurry is stirred for an additional 18 hours. The reaction mixture is poured into 800 mL of ice cold water, extracted with 3×500 mL methylene chloride, the extracts then combined and dried with anhydrous magnesium sulfate and then filtered, and the filtrate then concentrated first by rotary evaporation and then by evaporated under high vacuum to remove nitromethane. The resulting residue is dissolved first in hot methylene chloride (70 mL) followed by hot hexanes (50 mL). The resulting solution is allowed to cool to r.t. and then placed in a refrigerator overnight. The solids formed are isolated and washed with cold hexanes and then dried under high vacuum to yield 10.80 g (32.0%) of off-white crystals. ¹H NMR shows the product to be as desired.

Step 2: Preparation of 2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenol

To a stirred solution of 10.30 g (50.00 mmol) of 4-(2,4,4-trimethylpentan-2-yl)phenol in 125 mL of methanol at 0° C. are added 7.48 g (50.00 mmol) of NaI and 2.00 g (50 mmol) of NaOH. To the resulting mixture is added 86 mL of a 5% aqueous NaOCl solution (commercial bleach) over a one hour period. The resulting slurry is stirred for one more hour at 0° C. Aqueous 10% Na₂S₂O₃ solution (30 mL) is added and acidified by addition of dilute hydrochloric acid. The resulting mixture is extracted with methylene chloride and the resulting organic layer is washed with brine and dried over anhydrous magnesium sulfate. Volatiles are removed and the resulting residue is purified by flash chromatography on silica gel, eluting with 5 volume percent (vol %) ethyl acetate in hexanes to yield 11.00 g (66%) of product as a viscous oil. ¹H NMR shows the product is as desired.

Step 3: Preparation of Intermediate, 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran

To a stirred solution of 4.91 g (14.78 mmol) of 4-(2,4,4-trimethylpentan-2-yl)phenol and 1.50 g (17.83 mmol) of 3,4-dihydropyran in 5 mL of methylene chloride at 0° C. is added 0.039 g (0.205 mmol) of para-toluenesulfonic acid monohydrate. The resulting solution quickly becomes purple. Solution is allowed to warm to r.t. and stirred for approximately 10 minutes. Triethylamine is added (0.018 g, 0.178 mmol) and the resulting mixture turns yellow. The mixture is diluted with 50 mL of methylene chloride, and successively washed with 50 mL each of 1M NaOH, water, and brine. The organic phase is dried with anhydrous magnesium sulfate, filtered, and the filtrate concentrated to give a crude material. The crude material is purified by flash chromatography on silica gel using 5 vol % ethyl acetate in hexanes to yield 5.18 g (93.12%) of product as a golden oil. ¹H NMR shows product is as desired

Step 4: Preparation of Intermediate, 3,6-di-tert-butyl-9-(2-(tetrahydro-2H-pyran-2-yloxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole

To a 50 mL three necked round bottom flask equipped with a stir bar and condenser under N₂ atmosphere are added 20 mL of dry toluene, 5.00 g (12.01 mmol) of 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran, 3.56 g (12.01 mmol) of di-t-butyl carbazolel), 0.488 g (2.56 mmol) of CuI, 7.71 g (36.22 mmol) of K₃PO₄, and 0.338 g (3.84 mmol) of N,N′-dimethylethylenediamine. Reaction mixture is refluxed for 48 hours, cooled, filtered through a bed of silica gel, the silica gel being then rinsed with tetrahydrofuran (THF), and the organics are concentrated to give a crude residue. Crude residue is crystallized from acetonitrile to yield 4.57 g (67.01%) of product as a white solid. ¹H NMR shows product is as desired.

Step 5: Preparation of 1,2-bis(4-fluoro-2-iodo-6-methylphenoxy)ethane

To a round bottom flask under N₂ atmosphere are added 10.33 g (40.99 mmol) of 2-iodo-4-fluoro-6-methylphenol, 11.34 g (82.05 mmol) of K₂CO₃, 80 mL of DMF, and 7.59 g (20.49 mmol) of ethylene glycol ditosylate (obtained from Aldrich). The reaction mixture is stirred and refluxed for 18 hours, cooled and concentrated. The residue is treated with 50/50 methylene chloride and water until all solids are dissolved and then the mixture is transferred to a separation funnel where the compound is extracted into methylene chloride. The organic solution is washed with 2N NaOH, water, and then brine, dried over anhydrous magnesium sulfate, filtered through a pad of silica gel and concentrated to give 9.93 g (91.4%) of a white solid. ¹H NMR shows the product is as desired.

Step. 6: Preparation of 2′,2″″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-3′-methyl-5-(2,4,4- trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol)

To a stirred solution of 5.0 g (8.82 mmol) of 3,6-di-tert-butyl-9-(2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole in 75 mL of tetrahydrofuran at 0° C. under nitrogen atmosphere, 8.1 mL (20.25 mmol) of n-butyllithium (2.5 M solution in hexanes) is added over a period of 10 minutes. The solution is stirred at 0° C. for three more hours. Tri-isopropyl borate (4.8 mL, 20.8 mmol) is added to this and stirring is continued at 0° C. for 1 hour. The mixture is slowly warmed to r.t. and stirred for 3 more hours at r.t. The reaction mixture is concentrated to dryness by rotary evaporation and 100 mL of ice cold water is added. The mixture is acidified using 2N hydrochloric acid and extracted with methylene chloride. The methylene chloride solution is washed with water and brine. The solvent is removed by rotary evaporation and the residue is dissolved in 90 mL of dimethoxyethane. This solution is then treated with a solution of 1.06 g (26.5 mmol) of NaOH in 25 mL of water, 25 mL of tetrahydrofuran and 2.2 g (4.15 mmol) of 1,2-bis(4-fluoro-2-iodo-6-methylphenoxy)ethane. The system is purged with nitrogen and 0.30 g (0.26 mmol) of Pd(PPh₃)₄ was added. The mixture is then heated to 85° C. for 36 hours under nitrogen atmosphere. The precipitated product is collected by filtration. The solid thus obtained is dissolved in methylene chloride, washed with brine, and dried over anhydrous magnesium sulfate. After removal of the solvent, the reaction products are dissolved in 150 mL of THF/MeOH (1:1) and stirred for 5 hours at 50° C. after the addition of 100 mg of PTSA. The solvent is removed and the solid obtained is dissolved in 300 mL of 10% ethyl acetate in hexanes. This solution is passed through a small bed of silica gel. Removal of the solvent followed by drying under reduced pressure gives 4.65 g (85%) of the pure ligand as a white solid. ¹H NMR shows the product to be as desired.

Step 7: Preparation of 1,2-bis(4-fluoro-2-iodophenoxy)ethane

To a round bottom flask under N₂ atmosphere is added 3.00 g (12.61 mmol) of 2-iodo-4-fluorophenol, 3.49 g (25.25 mmol) of K₂CO₃, 25 mL of DMF, and 2.34 g (6.32 mmol) of ethylene glycol ditosylate. The reaction mixture was refluxed for 18 hours, cooled and concentrated. The residue was treated with 50/50 methylene chloride and water until all solids were dissolved and then transferred the mixture to a separation funnel where the compound was extracted into methylene chloride. The organic solution was washed with 2N, NaOH, water then brine, dried over anhydrous magnesium sulfate, filtered through a pad of silica gel and concentrated to give 3.07 g (97.0%) of pure bridge compound (1,2-bis(4-fluoro-2-iodophenoxy)ethane) as a white solid. ¹H NMR shows the product to be as desired.

Step 8: Preparation of 6′,6″″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-fluoro-5-(2,4,4-trimethylpentan-2-yl)- [1,1′-biphenyl]-2-ol)

To a stirred solution of 2.5 g (4.41 mmol) of 3,6-di-tert-butyl-9-(2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole in 40 mL of tetrahydrofuran at 0° C. under nitrogen atmosphere 4.05 mL (10.12 mmol) of n-butyllithium (2.5 M solution in hexanes) is added over a period of 10 minutes. The solution is stirred at 0° C. for three more hours. Tri-isopropyl borate (2.4 mL, 10.4 mmol) is added to this and stirring continued at 0° C. for 1 hour. The mixture is slowly warmed to r.t. and stirred for 3 more hours at r.t. The reaction mixture is concentrated to dryness by rotary evaporation and 100 mL of ice cold water is added. The mixture is acidified using 2N hydrochloric acid and extracted with methylene chloride. The methylene chloride solution is washed with water and brine. The solvent is removed by rotary evaporation and the residue is dissolved in 50 mL of dimethoxyethane. This solution is then treated with a solution of 0.53 g (13.25 mmol) of NaOH in 15 mL of water, 15 mL of tetrahydrofuran and 1.05 g (2.09 mmol) of 1,2-bis(4-fluoro-2-iodophenoxy)ethane. The system is purged with nitrogen and 0.15 g (0.13 mmol) of Pd(PPh₃)₄ is added. The mixture is then heated to 85° C. for 36 hours under nitrogen atmosphere. The reaction mixture is cooled and the volatiles are removed by rotary evaporation. The residue is treated with 100 mL of water and extracted with methylene chloride. The methylene chloride solution is washed with water and brine, and dried over anhydrous magnesium sulfate. After removal of the solvent, the reaction products are dissolved in 100 mL of THF/MeOH (1:1) and stirred for 5 hours at 50° C. after the addition of 50 mg of PTSA. The solvent is removed and the product is purified by flash chromatography eluting with 5% ethyl acetate in hexanes to obtain 2.2 g (82.4%) of the ligand as white solid. ¹H NMR shows the product to be as desired.

Metal-Ligand Complex 1

Step 9: Preparation of (6′,6″-(ethane-1,2-diylbis(oxy))bis(3′-fluoro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl-5-(2,4,4-trimethylpentan-2- yl)biphenyl)dimethyl-halfnium (Metal-Ligand Complex 1)

To a 1.571 g (1.29 mmol) of 6′,6″″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol) and 0.415 g (1.29 mmol) of HfCl₄ suspended in 35 mL of toluene is added 1.94 mL (5.82 mmol) of 3M diethyl ether solution of MeMgBr. After stirring for 2 hr at ambient temperature, solvent is removed under reduced pressure. To the residue are added 20 mL of toluene and 30 mL hexane and suspension is filtered. Solvent is removed under reduced pressure, leaving an off-white solid. To the residue is added 30 mL of hexane and suspension is stirred for 20 min. White solid is collected on the frit, washed, with 4 mL of cold hexane and dried under reduced pressure to give 1.07 g of product. The filtrate is put into freezer (−30° C.) for 3 days. Solvent is decanted and the resulting crystals are washed with cold hexane (2×3 mL) and dried under reduced pressure to obtain 345 mg of additional material. Combined yield 1.415 g (77%). ¹H NMR shows the product to be as desired.

Metal-Ligand Complex 2

Alternative Step 9: Preparation of (6′,6″-(ethane-1,2-diylbis(oxy))bis(3′-fluoro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl)dimethyl-zirconium (Metal-Ligand Complex *2. *Further Data Relating to this Complex is not Included in the Examples Below.)

To a mixture of 6′,6″″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol) (1.989 g, 1.64 mmol) and ZrCl₄ (0.382 g, 1.64 mmol) in 50 mL of toluene is added 2.57 mL of 3M solution of MeMgBr in diethyl ether. After stirring for 1 hr solvent is removed under reduced pressure. To the residue is added 30 mL of toluene followed by 30 mL of hexane and solution is filtered giving colorless solution. Solvent is removed under reduced pressure, giving a colorless solid. To this solid is added 20 mL of hexane, dissolving the residue. Solvent is removed under reduced pressure. To the residue is added 15 mL of hexane and suspension is stirred for 1 hour. Solid is collected on the frit, washed with 5 mL of cold hexane and dried under reduced pressure to give 1.223 g of product. Yield 56.0%. ¹H NMR shows product to be as desired.

Metal-Ligand Complex 3 Alternative Step 9: Preparation of (2′,2″-(ethane-1,2-diylbis(oxy))bis(5′-fluoro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4- trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-halfnium (Metal-Ligand Complex 3).

To a cold (−25° C.) suspension of 2′,2″″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol) (3.03 g, 2.44 mmol) and HfCl₄ (0.782 g, 2.44 mmol) in 70 mL of toluene is added 3.5 mL (10.5 mmol) of 3M diethyl ether solution of MeMgBr. After stirring for 1 hr solvent is removed under reduced pressure. To the residue is added 20 mL of toluene followed by 30 mL of hexane. The suspension is filtered, giving a gray solution. The solvent is removed under reduced pressure, leaving a light gray solid. The residue is suspended in 8 mL of hexane and suspension is stirred for 30 min. The solid is collected on the frit, washed with 3 mL of hexane and dried under reduced pressure to give 2.87 g of product as off-white solid. Yield is 81.2%. ¹H NMR shows product is as desired.

Metal-Ligand Complex 4 Alternative Step 9: Preparation of (2′,2″-(ethane-1,2-diylbis(oxy))bis(5′-fluoro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-methyl-5-(2,4,4- trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-zirconium (Metal-Ligand Complex 4).

To a suspension of 2′,2″″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol) (0.75 g, 0.59 mmol) and ZrCl₄ (0.137 g, 0.59 mmol) in 50 mL of toluene is added 0.84 mL (2.53 mmol) of 3M diethyl ether solution of MeMgBr. After stirring for 1 hr solvent is removed under reduced pressure. To the residue is added 20 mL of toluene followed by 30 mL of hexane. Suspension is filtered giving colorless solution. Solvent is removed under reduced pressure, leaving a white solid. The residue is suspended in 15 mL of hexane and suspension is stirred for 30 min. The solid is collected on the frit, washed with 3 mL of hexane and dried under reduced pressure to give 0.545 g of product as white solid. Yield is 66.5%. ¹H NMR shows product is as desired.

Polymerization Procedure

Polymerizations are conducted in a 2 L Parr™ batch reactor. The reactor is heated by an electrical heating mantle, and is cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating/cooling system are controlled and monitored by a Camile™ TG process computer. The bottom of the reactor is fitted with a dump valve, which empties the reactor contents into a stainless steel (SS) dump pot, which is prefilled with a catalyst kill solution (typically 5 mL of a IRGAFOX™/IRGANOX™/toluene mixture). The dump pot is vented to a 30 gallon blowdown tank, with both the pot and the tank N₂ purged. All chemicals used for polymerization or catalyst makeup are run through purification columns to remove any impurities that may affect polymerization. The 1-octene is passed through 2 columns, the first containing Al₂O₄ alumina, the second containing Q5 reactant to remove oxygen. The ethylene is also passed through 2 columns, the first containing Al₂O₄ alumina and 4 Angstroms (Å) pore size molecular sieves, the second containing Q5 reactant. The N₂, used for transfers, is passed through a single column containing Al₂O₄ alumina, 4 Å pore size molecular sieves and Q5 reactant.

The reactor is loaded first from the shot tank containing 1-octene, depending on desired reactor load. The shot tank is filled to the load set points by use of a lab scale to which the shot tank is mounted. After liquid feed addition, the reactor is heated up to the polymerization temperature set point. If ethylene is used, it is added to the reactor when at reaction temperature to maintain reaction pressure set point. Ethylene addition amounts are monitored by a micro-motion flow meter.

The catalyst and activators are mixed with the appropriate amount of purified toluene to achieve a desired molarity solution. The catalyst and activators are handled in an inert glove box, drawn into a syringe and pressure transferred into the catalyst shot tank.

This is followed by 3 rinses of toluene, 5 mL each.

Immediately after catalyst addition the run timer begins. If ethylene is used, it is then added by the Camile to maintain reaction pressure set point in the reactor. These polymerizations are run for 10 min., then the agitator is stopped and the bottom dump valve opened to empty reactor contents to the dump pot. The dump pot contents are poured into trays placed in a lab hood where the solvent is evaporated off overnight. The trays containing the remaining polymer are then transferred to a vacuum oven, where they are heated up to 140° C. under vacuum to remove any remaining solvent. After the trays cool to ambient temperature, the polymers are weighed for yield/efficiencies, and submitted for polymer testing.

Melting and crystallization temperatures of polymers are measured by differential scanning calorimetry (DSC 2910, TA Instruments, Inc.). Samples are first heated from r.t. to 210° C. at 10° C./min After being held at this temperature for 4 min, the samples are cooled to −40° C. at 10° C./min and are then heated to 215° C. at 10° C./min after being held at −40° C. for 4 min.

For ethylene/1-octene copolymers: Molecular weight distribution (Mw, Mn, PDI) information is determined by analysis on an Agilent 1100 Series Gel Permeation Chromatographer (GPC). Polymer samples are dissolved for at least 5 minutes at r.t. (˜25° C.) at a concentration of 25 mg/mL in tetrahydrofuran (THF), with brief vortexing after solvent addition but no further agitation. A 1 microliter (μL) aliquot of the sample is injected by the Agilent auto-sampler. The GPC utilized two (2) Polymer Labs PLgel 10 micrometer (μm) MIXED-D columns (300×7.5 mm) at a flow rate of 1.0 mL/min at 35° C. Sample detection is performed using a differential refractive index detector. A conventional calibration of narrow Polyethylene Glycol (PEG) standards (Mp Range: 106-21,030) is utilized, with data reported in PEG-apparent units.

Mass gas chromatography-mass spectrometry (GC/MS) is conducted in the electron impact (EI) and positive ion ammonia chemical ionization (NH₃—CI) modes. Instrumentation used is an Aglilent 6890N GC coupled to a Micromass GCT, SN CA095, time of flight GC/MS system in EI and PCI-NH3 modes. The following analysis conditions are used: Column is 30 m×0.250 mm (0.25 μm film) Rxi-5SilMS, temperature of column is from 100° C. (2 min) to 330° C. at 15° C./minute, injector at 320° C., GC re-entrant at 300° C., source at 180° C./120° C. (EI/CI), flow is 1.2 ml/min (He) (constant flow, split −50:1), detector is MCP 2400V, mode is +TOFMS, Lock Mass is 201.9609 C₆F₅Cl (+EI/+CI).

Examples 1-3

Using the Polymerization Procedure and the Metal-Ligand Complexes Synthesis Procedures for Metal-Ligand Complexes 1, 3, and 4, ethylene and 1-octene are copolymerized to form a poly(co-ethylene-α-olefin) dielectric fluid composition. Conditions of the polymerization, identification of the activating co-catalysts, and results are shown in Table 1 hereinbelow.

TABLE 1 Ethylene/1-Octene Copolymerization Metal- Ligand Ethylene Ethylene Efficiency Exam- Complex Pressure Consumed Yield (gPoly/ ple # Name moles (psi) (g) (g) gMetal) Mw 1 1 1 150 22.0 242.9 1,360,861 2162 2 3 3 70 12.6 149.5 279,194 958 3 4 3 70 37.6 376.3 1,375,004 602 Polymerization conditions: temp: 140° C.; 650 g of 1-octene; pre-catalyst:activator = 1:1.2; activator: [HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄]; 15 mols of MMAO; reaction time 10 min.

activator: [HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄]; 15 mols of MMAO; reaction time 10 min

Comparative Example A

Testing to determine neutralization number, pour point, and fire point is carried out on the dielectric fluid compositions of Examples 1-3 and also mineral oil, which is designated as Comparative Example A. The results are shown in Table 2.

TABLE 2 Characterization of dielectric fluids from Table 1 and Comparative Example A Neutralization Pour Fire Number, mg Point Point Example # KOH/g (° C.) (° C.) Mw 1 0.03 −33 320 2162 2 0.01 −52 210 958 3 0.01 −58 602 Comp. 0.01 −50 150 Ex. A

Example 4

Ethylene and 1-octene are again copolymerized using the Polymerization Procedure and Metal-Ligand Complex 3 Synthesis Proce. Conditions and identification of activating co-catalyst are shown in Table 3 hereinbelow. GC chromatographic analysis, illustrating one embodiment of the extensive isomer formation that characterizes the inventive dielectric fluid compositions, is shown in FIG. 1.

TABLE 3 Ethylene/1-Octene Copolymerization Ex- Ethylene Ethylene Efficiency am- Catalyst Pressure Con- Yield (gPoly/ ple # Name □moles (psi) sumed (g) (g) gMetal) Mw 4 3 2 100 44.2 195 431,677 1,170 Polymerization conditions: temp: 100° C.; 750 g of 1-octene; pre-catalyst: activator: 1 mmol of MMAO; reaction time 30 min.

Examples 5-6

A poly-α-olefin dielectric fluid composition is prepared, using the Polymerization Procedure and the Metal-Ligand Complexes 3 and 4 Synthesis Procedures. Results are shown in Table 4, and GC-MS chromatographic analysis of Example 5 is shown in FIG. 2.

TABLE 4 1-Octene Polymerization Catalyst Efficiency Example # Name □moles Yield (g) (gpoly/gMetal) Mw 5 3 15 130.7 48,817 1,610 6 4 15 81.4 52,837 960 Polymerization conditions: temp: 140° C.; 650 g of 1-octene; pre-catalyst:activator = 1:1.2; activator: [HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄]; 20 mol of MMAO; reaction time 10 min.; 

What is claimed is:
 1. A method of using a dielectric fluid composition comprising a poly-α-olefin or a poly(co-ethylene/α-olefin) having a weight average molecular weight more than 200 and less than 5,000 daltons (Da) prepared from a process including a step of contacting together (1) a monomer selected from (a) an α-olefin; or (b) a combination of an α-olefin and ethylene; and (2) a catalytic amount of a catalyst wherein the catalyst includes a mixture or reaction product of ingredients (2a) and (2b) that is prepared before the contacting step, wherein ingredient (2a) is at least one metal-ligand complex of formula (I):

wherein M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; n is an integer of from 0 to 3, wherein when n is 0, X is absent; each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic, or two X are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral; each Z independently is O, S, N(C₁-C₄₀)hydrocarbyl, or P(C₁-C₄₀)hydrocarbyl; L is (C₁-C₄₀)hydrocarbylene or (C₁-C₄₀)heterohydrocarbylene, wherein the (C₁-C₄₀)hydrocarbylene has a portion that comprises a 2-carbon atom linker backbone linking the Z atoms in formula (I) and the (C₁-C₄₀)heterohydrocarbylene has a portion that comprises a 2-atom atom linker backbone linking the Z atoms in formula (I), wherein each atom of the 2-atom linker of the (C₁-C₄₀)heterohydrocarbylene independently is a carbon atom or a heteroatom, wherein each heteroatom independently is O, S, S(O), S(O)₂, Si(R^(C))₂, Ge(R^(C))₂, P(R^(P)), or N(R^(N)), wherein independently each R^(C) is unsubstituted (C₁-C₁₈)hydrocarbyl or the two R^(C) are taken together to form a (C₂-C₁₉)alkylene, each R^(P) is unsubstituted (C₁-C₁₈)hydrocarbyl; and each R^(N) is unsubstituted (C₁-C₁₈)hydrocarbyl, a hydrogen atom or absent; R^(1a), R^(2a), R^(1b), and R^(2b) independently is a hydrogen, (C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, N(R^(N))₂, NO₂, OR^(C), SR^(C), Si(R^(C))₃, Ge(R^(C))₃, CN, CF₃, F₃CO, halogen atom; and each of the others of R^(1a), R^(2a), R^(1b), and R^(2b) independently is a hydrogen, (C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, N(R^(N))₂, NO₂, OR^(C), SR^(C), Si(R^(C))₃, CN, CF₃, F₃CO or halogen atom; each of R^(3a), R^(4a), R^(3b), R^(4b), R^(6c), R^(7c), R^(8c), R^(6d), R^(7d), and R^(8d) independently is a hydrogen atom; (C₁-C₄₀)hydrocarbyl; (C₁-C₄₀)heterohydrocarbyl; Si(R^(C))₃, Ge(R^(C))₃, P(R^(P))₂, N(R^(N))₂, OR^(C), SR^(C), NO₂, CN, CF₃, R^(C)S(O)—, R^(C)S(O)₂—, (R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—, R^(C)C(O)N(R)—, (R^(C))₂NC(O)— or halogen atom; each of R^(5c) and R^(5d) independently is a (C₆-C₄₀)aryl or (C₁-C₄₀)hetero-aryl; each of the aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, hydrocarbylene, and hetero-hydrocarbylene groups independently is unsubstituted or substituted with one or more substituents R^(S); and each R^(S) independently is a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted (C₁-C₁₈)alkyl, F₃C—, FCH₂O—, F₂HCO—, F₃CO—, R₃Si—, R₃Ge—, RO—, RS—, RS(O)—, RS(O)₂—, R₂P—, R₂N—, R₂C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R₂NC(O)—, or two of the R^(S) are taken together to form an unsubstituted (C₁-C₁₈)alkylene, wherein each R independently is an unsubstituted (C₁-C₁₈)alkyl; and wherein ingredient (2b) is at least one activating co-catalyst, such that the ratio of total number of moles of the at least one metal-ligand complex (2a) to total number of moles of the at least one activating co-catalyst (2b) is from 1:10,000 to 100:1; under conditions such that a product selected from a poly-α-olefin and a poly(co-ethylene-α-olefin) is formed, the product having molecular weight distribution components and a backbone weight average molecular weight (Mw) that are more than 200 Da and less than 5,000 Da, the product including at least two isomers in each distribution component above 300 Da, the method comprising operating at least one of (1) a transformer containing a transformer oil comprising the dielectric fluid composition; (2) a bushing or a transmission or distribution cable containing an insulation fluid comprising the dielectric fluid composition; (3) a switchgear containing a switchgear fluid comprising the dielectric fluid composition; and (4) a telecommunications cable, electronic device, or electrical apparatus containing the dielectric fluid composition.
 2. The method of claim 1 wherein the weight average molecular weight of the poly-α-olefin or poly(co-ethylene/α-olefin) is less than 1500 daltons.
 3. The method of claim 1, wherein each Z of the metal-ligand complex of formula (I) is O.
 4. The method of claim 1, wherein R^(1a) and R^(1b) of the metal-ligand complex of formula (I) are methyl, ethyl or isopropyl.
 5. The method of claim 1, wherein R^(1a) and R^(1b) of the metal-ligand complex of formula (I) are fluorine atoms, chlorine atoms, bromine atoms or iodine atoms.
 6. The method of claim 1, wherein L of the metal-ligand complex of formula (I) is —CH₂CH₂—, —CH(CH₃)CH(CH₃)—, 1,2-cyclopentane-diyl or 1,2-cyclohexane-diyl.
 7. The method of claim 1, wherein R^(5d) of the metal-ligand complex of formula (I) independently is a 2,7-disubstituted 9H-carbazol-9-yl or a 3,6-disubstituted 9H-carbazol-9-yl, 9H-carbazol-9-yl, wherein each substituent is R^(S).
 8. The method of claim 1, wherein R^(5d) of the metal-ligand complex of formula (I) independently is a (C₆-C₄₀)aryl that is a 2,4-disubstituted phenyl, wherein each substituent is R^(S); 2,5-disubstituted phenyl wherein each substituent is R^(S); 2,6-disubstituted phenyl wherein each substituent is R^(S); 3,5-disubstituted phenyl wherein each substituent is R^(S); 2,4,6-trisubstituted phenyl wherein each substituent is R^(S); naphthyl or substituted naphthyl wherein each substituent is R^(S); 1,2,3,4-tetrahydronaphthyl; anthracenyl; 1,2,3,4-tetrahydro-anthracenyl; 1,2,3,4,5,6,7,8-octahydroanthracenyl; phenanthrenyl; or 1,2,3,4,5,6,7,8-octahydrophen-anthrenyl.
 9. The method of claim 1, wherein the contacting of the monomer and the catalyst is at conditions that include a temperature ranging from 40° C. to 300° C.
 10. An article selected from the group consisting of (1) a transformer containing a transformer oil comprising the dielectric fluid composition of claim 1; (2) a bushing or a transmission or distribution cable containing an insulation fluid comprising the dielectric fluid composition of claim 1; (3) a switchgear containing a switchgear fluid comprising the dielectric fluid composition of claim 1; and (4) a telecommunications cable, electronic device, or electrical apparatus containing the dielectric fluid composition of claim
 1. 